Golf ball layers formed of polyurethane-based and polyurea-based compositions incorporating block copolymers

ABSTRACT

Golf equipment having improved cut and shear resistance that includes a polyurea-based composition or polyurethane-based composition, preferably saturated and/or water resistant, formed of a prepolymer, a functionalized block copolymer, and optionally further cured or chain extended with a curing agent, where the prepolymer is incorporated at the terminal end of the functionalized block copolymer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.10/900,468, filed Jul. 28, 2004, now pending, which is acontinuation-in-part of U.S. patent application Ser. No. 10/409,092,filed Apr. 9, 2003, now U.S. Pat. No. 6,964,621, which is acontinuation-in-part of U.S. patent application Ser. No. 10/066,637,filed Feb. 6, 2002, now U.S. Pat. No. 6,582,326, which is a continuationof U.S. patent application Ser. No. 09/453,701, filed Dec. 3, 1999, nowU.S. Pat. No. 6,435,986; and also a continuation-in-part of U.S. patentapplication Ser. No. 10/228,311, filed Aug. 27, 2002, now U.S. Pat. No.6,835,794, which is a continuation-in-part of U.S. patent applicationSer. No. 09/466,434, filed Dec. 17, 1999, now U.S. Pat. No. 6,476,176,and a continuation-in-part of U.S. patent application Ser. No.09/951,963, filed Sep. 13, 2001, now U.S. Pat. No. 6,635,716, and alsoclaims priority to U.S. Patent Provisional Application No. 60/401,047,filed Aug. 6, 2002. The entire disclosures of these applications areincorporated by reference herein.

FIELD OF THE INVENTION

The invention relates to golf equipment including polyurethane-basedcompositions incorporating block copolymers, polyurea-based compositionsincorporating block copolymers, and mixtures thereof. In particular, thepresent invention is directed to golf equipment including compositionsformed from the reaction product of an isocyanate and a functionalizedblock copolymer. In addition, the compositions of the present inventionmay be formed from the reaction product of a prepolymer, which is basedon an isocyanate and a polyol or amine, and a functionalized blockcopolymer. The compositions of the invention may also be formed byreacting an excess of prepolymer, which is based on an isocyanate and apolyol or amine, with a functionalized block copolymer to form anintermediate prepolymer having the block copolymer portion capped withisocyanate groups at each end, which is then reacted with a curing agentto form a polyurethane-based or polyurea-based composition.

BACKGROUND OF THE INVENTION

Golf equipment, i.e., clubs and balls, are formed from a variety ofcompositions. For example, golf ball covers are formed from a variety ofmaterials, including balata and ionomer resins. Balata is a natural orsynthetic trans-polyisoprene rubber. Balata covered balls are favored bymore highly skilled golfers because the softness of the cover allows theplayer to achieve spin rates sufficient to more precisely control balldirection and distance, particularly on shorter shots.

However, balata covered balls are easily damaged, and thus lack thedurability required by the average golfer. Accordingly, alternativecover compositions have been developed in an attempt to provide ballswith spin rates and a feel approaching those of balata covered balls,while also providing a golf ball with a higher durability and overalldistance.

Ionomer resins have, to a large extent, replaced balata as a covermaterial. Chemically, ionomer resins are a copolymer of an olefin and anα,β-ethylenically-unsaturated carboxylic acid having 10 to 90 percent ofthe carboxylic acid groups neutralized by a metal ion, as disclosed inU.S. Pat. No. 3,264,272. Commercially available ionomer resins include,for example, copolymers of ethylene and methacrylic or acrylic acid,neutralized with metal salts. Examples of commercially available ionomerresins include, but are not limited to, SURLYN® from DuPont de Nemoursand Company, and ESCOR® and IOTEK® from Exxon Corporation. These ionomerresins are distinguished by the type of metal ion, the amount of acid,and the degree of neutralization.

U.S. Pat. Nos. 3,454,280, 3,819,768, 4,323,247, 4,526,375, 4,884,814,and 4,911,451 all relate to the use of SURLYN®-type compositions in golfball covers. However, while SURLYN® covered golf balls, as described inthe preceding patents, possess virtually cut-proof covers, the spin andfeel are inferior compared to balata covered balls.

Polyurethanes have also been recognized as useful materials for golfball covers since about 1960. U.S. Pat. No. 3,147,324 is directed to amethod of making a golf ball having a polyurethane cover. The resultinggolf balls are durable, while at the same time maintaining the “feel” ofa balata ball.

Various companies have investigated the usefulness of polyurethane as agolf ball cover material. U.S. Pat. No. 4,123,061 teaches a golf ballmade from a polyurethane prepolymer formed of polyether withdiisocyanate that is cured with either a polyol or an amine-type curingagent. U.S. Pat. No. 5,334,673 discloses the use of two categories ofpolyurethane available on the market, i.e., thermoset and thermoplasticpolyurethanes, for forming golf ball covers and, in particular,thermoset polyurethane covered golf balls made from a composition ofpolyurethane prepolymer and a slow-reacting amine curing agent, and/or aglycol.

Unlike SURLYN® covered golf balls, polyurethane golf ball covers can beformulated to possess the soft “feel” of balata covered golf balls.However, golf ball covers made from polyurethane have not, to date,fully matched SURLYN® golf balls with respect to resilience or therebound of the golf ball cover, which is a function of the initialvelocity of a golf ball after impact with a golf club.

Furthermore, because the polyurethanes used to make the covers of suchgolf balls generally contain an aromatic component, e.g., aromaticdiisocyanate, polyol, or polyamine, they are susceptible todiscoloration upon exposure to light, particularly ultraviolet (UV)light. To slow down the discoloration, light and UV stabilizers, e.g.,TINUVIN® 770, 765, and 328, are added to these aromatic polymericmaterials. However, to further ensure that the covers formed fromaromatic polyurethanes do not appear discolored, the covers are paintedwith white paint and then covered with a clear coat to maintain thewhite color of the golf ball. The application of a uniform whitepigmented coat to the dimpled surface of the golf ball is a difficultprocess that adds time and costs to the manufacture of a golf ball.

In addition, while certain polyols provide more stability to thepolyurethane polymer in terms of moisture resistance, polyurethanesremain highly susceptible to changes in their physical properties due toabsorption of moisture. To avoid moisture absorption, manufacturers haveattempted to use moisture barrier layers, e.g., U.S. Pat. No. 5,820,488,located between the core and the cover. However, there still remains aneed for materials that are resistant to absorption of moisture suitablefor forming a golf ball component.

Polyureas have also been proposed as cover materials for golf balls. Forinstance, U.S. Pat. No. 5,484,870 discloses a polyurea compositioncomprising the reaction product of an organic isocyanate and an organicamine, each having at least two functional groups. Once these twoingredients are combined, the polyurea is formed, and thus the abilityto vary the physical properties of the composition is limited. Likepolyurethanes, polyureas are not completely comparable to SURLYN® golfballs with respect to resilience or the rebound or damping behavior ofthe golf ball cover.

Therefore, there remains a continuing need for golf equipment havingsoft components that provide improved resilience, increased cut, scratchand abrasion resistance, moisture resistance, and enhanced adherencewithout adversely affecting overall performance characteristics of thegolf balls. Thus, it would be advantageous to provide a composition thatcombines the cut and scratch resistance with improved resistance todiscoloration and moisture that are suitable for forming golf ballcomponents and other golf-related equipment.

SUMMARY OF THE INVENTION

The present invention is generally directed to golf equipment having atleast a portion formed of a polyurea composition. In one embodiment, thepresent invention is directed to one-piece golf balls includingpolyurea. In another embodiment, the compositions of the invention areused in two-piece and multi-component, e.g., three-piece, four-piece,etc. golf balls including at least one cover layer and a core, whereinat least one cover layer includes at least one polyurea, as well asmulti-component golf balls including cores and/or covers having two ormore layers, wherein at least one such layer(s) is formed of at leastone polyurea.

For example, one aspect of the invention is directed to a golf ballhaving a core and a cover, wherein the cover is formed from a reactiveproduct composition including an isocyanate and an amine-terminatedcompound selected from the group consisting of:

and mixtures thereof, wherein n, x, y, and z are about 1 or greater,preferably about 1 to about 20, wherein R is an alkyl group having about1 to about 20 carbon atoms, preferably about 1 to about 12 carbon atoms,a phenyl group; a cyclic group; or mixtures thereof, wherein R₁ and R₂are alkylene groups having about 1 to about 20 carbon atoms, preferablyabout 1 to about 12 carbon atoms, phenylene groups, cyclic groups, ormixtures thereof, and wherein R₃ is a hydrogen, a methyl group, or amixture thereof.

In one embodiment, the composition includes linkages having the generalformulae:

or mixtures thereof, wherein x is the chain length, i.e., about 1 orgreater, and wherein R and R₁ are straight chain or branched hydrocarbonchains having about 1 to about 20 carbons. In another embodiment, thecomposition includes only linkages having the general formula:

wherein x is the chain length, i.e., about 1 or greater, and wherein Rand R₁ are straight chain or branched hydrocarbon chains having about 1to about 20 carbons.

The composition may further include a curing agent selected from thegroup consisting of hydroxy-terminated curing agents, amine-terminatedcuring agents, and mixtures thereof. In one embodiment, theamine-terminated curing agent is a secondary diamine curing agent. Inanother embodiment, the amine-terminated curing agents are selected fromthe group consisting of ethylene diamine; hexamethylene diamine;1-methyl-2,6-cyclohexyl diamine; 2,2,4- and2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;N,N′-diisopropyl-isophorone diamine;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis-(methylamine);1,3-cyclohexane-bis-(methylamine); diethylene glycol bis-(aminopropyl)ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylene tetramine; tetraethylene pentamine; propylenediamine; 1,3-diaminopropane; dimethylamino propylamine; diethylaminopropylamine; imido-bis-(propylamine); monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; polyoxypropylene diamine; propylene oxide-basedtriamine; 3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixturesthereof.

The cover preferably has a difference in yellowness index (ΔYI) of about12 or less after 5 days of ultraviolet light exposure. In addition, thecover preferably has a difference in b chroma dimension of about 6 orless after 5 days of ultraviolet light exposure.

In one embodiment, the composition may include at least onedensity-adjusting filler.

The present invention is also directed to a golf ball including a core,a layer, which may include at least one thermoplastic or thermosetnon-ionomeric material, disposed about the core to create an inner ball,and a cover cast onto the inner ball, wherein the cover includes a lightstable polyurea material including at least one isocyanate, at least oneamine-terminated compound, and at least one curing agent comprising ahydroxy-terminated curing agent, an amine-terminated curing agent, or amixture thereof. The amine-terminated compound may be selected from thegroup consisting of amine-terminated hydrocarbons, amine-terminatedpolyethers, amine-terminated polyesters, amine-terminatedpolycaprolactones, amine-terminated polycarbonates, amine-terminatedpolyamides, and mixtures thereof. In one embodiment, theamine-terminated compound comprises primary amines, secondary amines,triamines, or combinations thereof.

In another embodiment, the cover has a thickness of about 0.02 inches toabout 0.035 inches. In yet another embodiment, the layer has a firstShore D hardness and the cover has a second Shore D hardness, andwherein the ratio of second Shore D hardness to the first Shore Dhardness is about 0.7 or less. In still another embodiment, the core hasa diameter of about 1.55 or greater.

The inner ball may include a moisture barrier layer. In one embodiment,the inner ball is surface treated.

The present invention also relates to a golf ball including a core, anintermediate layer having a hardness of about 60 Shore D or greater, anda cover formed of a polyurea material comprising at least one isocyanateand at least one amine-terminated compound, wherein the cover has ahardness of about 30 Shore D to about Shore 60, and wherein the golfball has a COR of about 0.800 or greater.

The amine-terminated compound is selected from the group consisting ofamine-terminated hydrocarbons, amine-terminated polyethers,amine-terminated polyesters, amine-terminated polycaprolactones,amine-terminated polycarbonates, amine-terminated polyamides, andmixtures thereof. In addition, the polyurea material may further includea curing agent selected from the group consisting of ahydroxy-terminated curing agent, an amine-terminated curing agent, andmixtures thereof.

In one embodiment, the ratio of the cover hardness to the intermediatelayer hardness is about 0.7 or less. In another embodiment, the coverhas a thickness of about 0.2 inches to about 0.035 inches.

In still another embodiment, the intermediate layer includes anionomeric material. In an alternate embodiment, the intermediate layercomprises a thermoset non-ionomeric material, a thermoplasticnon-ionomeric material, or mixtures thereof.

The present invention is also directed to a golf ball including at leasta cover and at least one core layer wherein the cover is formed from acomposition including at least one polyurea composition formed from apolyurea prepolymer, i.e., an isocyanate and an amine-terminatedcompound, cured with a curing agent.

The present invention is further directed to a golf ball including acover, a core and at least one intermediate layer interposed between thecover and an outermost core layer, wherein the intermediate layer isformed from a composition including a polyurea prepolymer, i.e., anisocyanate and an amine-terminated compound, cured with a curing agent

The present invention is yet further directed to a golf ball including acover, a core, and at least one intermediate layer interposed betweenthe cover and the core, wherein the outermost cover layer and at leastone intermediate layer are both formed from a polyurea compositionincluding a polyurea prepolymer, i.e., an isocyanate and anamine-terminated compound, cured with a curing agent.

In another embodiment of the present invention, the cover preferablyincludes from about 1 to about 100 weight percent of the polyurea, withthe remainder of the cover, if any, including at least one other polymerknown to one of ordinary skill in the art. In another embodiment, thecover preferably includes from about 1 to about 100 weight percent ofthe polyurea, with the remainder of the cover, if any, including one ormore compatible, resilient polymers such as would be known to one ofordinary skill in the art.

The invention is further directed to a golf ball including at least onelight stable cover layer formed from a composition including at leastone polyurea formed from a polyurea prepolymer and a curing agent. Inone embodiment, the polyurea prepolymer includes at least one isocyanateand at least one amine-terminated compound.

In this aspect of the invention, the isocyanate is saturated, andselected from the group consisting of ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate;octamethylene diisocyanate; decamethylene diisocyanate;2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylenediisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; methylcyclohexylene diisocyanate;2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate;4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate;1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl)dicyclohexane;2,4′-bis(isocyanatomethyl)dicyclohexane; isophoronediisocyanate;triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexanediisocyanate; dicyclohexylmethane diisocyanate; 4,4′-dicyclohexylmethanediisocyanate; 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluenediisocyanate; and mixtures thereof. The saturated diisocyanate ispreferably selected from the group consisting of isophoronediisocyanate,4,4′-dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate,or a combination thereof.

In another embodiment, the isocyanate is an aromatic aliphaticisocyanate selected from the group consisting of meta-tetramethylxylenediisocyanate; para-tetramethylxylene diisocyanate; trimerizedisocyanurate of a polyisocyanate; dimerized uretdione of apolyisocyanate; a modified polyisocyanate; and mixtures thereof.

The amine-terminated compound may be a polyether amine selected from thegroup consisting of polytetramethylene ether diamines, polyoxypropylenediamines, poly(ethylene oxide capped oxypropylene) ether diamines,triethyleneglycoldiamines, propylene oxide-based triamines,trimethylolpropane-based triamines, glycerin-based triamines, andmixtures thereof. In one embodiment, the polyether amine has a molecularweight of about 1000 to about 3000.

The curing agent may be selected from the group consisting ofhydroxy-terminated curing agents, amine-terminated curing agents, andmixtures thereof. In one embodiment, the hydroxy-terminated curingagents are selected from the group consisting of ethylene glycol;diethylene glycol; polyethylene glycol; propylene glycol;2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; dipropylene glycol;polypropylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol;2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylolpropane;cyclohexyldimethylol; triisopropanolamine;N,N,N′,N′-tetra-(2-hydroxypropyl)-ethylene diamine; diethylene glycolbis-(aminopropyl)ether; 1,5-pentanediol; 1,6-hexanediol;1,3-bis-(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexyldimethylol;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]cyclohexane;1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane;trimethylolpropane; polytetramethylene ether glycol, preferably having amolecular weight from about 250 to about 3900; and mixtures thereof.

The amine-terminated curing agents may be selected from the groupconsisting of ethylene diamine; hexamethylene diamine;1-methyl-2,6-cyclohexyl diamine; 2,2,4- and2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis-(methylamine);1,3-cyclohexane-bis-(methylamine); diethylene glycolbis-(aminopropyl)ether; 2-methylpentamethylene-diamine;diaminocyclohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; propylene diamine; 1,3-diaminopropane;dimethylamino propylamine; diethylamino propylamine;imido-(bis-propylamine); monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; and mixtures thereof.

In one embodiment, the composition further includes a catalyst selectedfrom the group consisting of a bismuth catalyst, zinc octoate,bis-butyltin dilaurate, bis-butyltin diacetate, tin (II) chloride, tin(IV) chloride, bis-butyltin dimethoxide,dimethyl-bis[1-oxonedecyl)oxy]stannane, di-n-octyltin bis-isooctylmercaptoacetate, triethylenediamine, triethylamine, tributylamine, oleicacid, acetic acid; delayed catalysts, and mixtures thereof. The catalystmay be present from about 0.005 percent to about 1 percent by weight ofthe composition.

In another embodiment, the cover layer has a difference in yellownessindex (ΔYI) of about 12 or less after 5 days of ultraviolet lightexposure. In yet another embodiment, the cover layer has a difference inb* dimension of about 6 or less after 5 days of ultraviolet lightexposure.

In this aspect of the invention, the cover layer may be formed fromcasting, injection molding, compression molding, reaction injectionmolding, and mixtures thereof, as well as other polymer processes knownto those of ordinary skill in the art.

The present invention is also directed to a golf ball including a core,a layer disposed about the core forming a center, and a cover cast ontothe center, wherein the cover comprises a light stable polyurea materialcomprising at least an isocyanate and an amine-terminated compound, andat least one of a hydroxy-terminated curing agent, a amine-terminatedcuring agent, or a mixture thereof.

In one embodiment, the layer includes ionomers, polyamides, highlyneutralized polymers, polyesters, polycarbonates, polyimides,polyolefins, acid copolymers, polyurethanes, vinyl resins, acrylicresins, polyphenylene oxide resins, metallocene-catalyzed polymers, andmixtures thereof. In another embodiment, the layer is a moisture barrierlayer.

In yet another embodiment, the cover has a thickness of about 0.02inches to about 0.035 inches. In addition, the layer preferably has afirst Shore D hardness and the cover has a second Shore D hardness,wherein the ratio of second Shore D hardness to the first Shore Dhardness is about 0.7 or less.

The core may include polybutadiene and may have a diameter of about 1.55or greater. In one embodiment, the core includes a cis-to-transcatalyst, a resilient polymer component, and a free radical source. Thecis-to-trans catalyst may include an organosulfur component, preferablyincluding a metal salt, a Group VIA component, an inorganic sulfidecomponent, an aromatic organic compound, or mixtures thereof.

In one embodiment, at least one of the core, the layer, the cover, orcombinations thereof comprise a density-adjusting filler.

The present invention is also directed to a method of forming a golfball including the steps of providing a golf ball center, mixing apolyurea prepolymer and at least one curing agent to form a castablereactive polyurea liquid material, filling a first set of mold halveswith a first amount of the material, lowering the center into the firstset of mold halves after a first predetermined time, wherein the centeris held by vacuum for a second predetermined time, and wherein thesecond predetermined time is sufficient for complete exothermic reactionof the first amount of material, releasing the center from the vacuumproviding a partially covered center, filling a second set of moldhalves with a second amount of the material, wherein the first andsecond amounts are substantially similar, and wherein an exothermicreaction of the second amount commences, and mating the second set ofmold halves with the partially covered center, wherein the exothermicreaction of the second amount concludes.

In one embodiment, the first predetermined time is about 40 seconds toabout 100 seconds. In another embodiment, the second predetermined timeis about 4 seconds to about 12 seconds.

The polyurea prepolymer may include at least one isocyanate and at leastone amine-terminated compound. In one embodiment, the step of mixing apolyurea prepolymer and at least one curing agent further includesmixing at least one triol or at least one tetraol, or mixtures thereof.In another embodiment, the step of mixing a polyurea prepolymer and atleast one curing agent further includes mixing at least one catalyst, atleast one light stabilizer, at least one defoaming agent, at least oneacid functionalized moiety, or combinations thereof.

In yet another embodiment, the step of providing a golf ball centerincludes the steps of providing a golf ball core and forming a layerdisposed about the golf ball core. In still another embodiment, the golfball core includes a polybutadiene reaction product, wherein the corehas a diameter of about 1.55 inches or greater, and wherein the layerhas a thickness of about 0.02 inches to about 0.035 inches.

The present invention is also directed to a golf ball having at leastone layer, formed of a water resistant polyurea or polyurethaneelastomer. In particular, this aspect of the invention relates to a golfball having at least one layer, such layer(s) being formed of a waterresistant polyurea or polyurethane. In one embodiment, a one-piece golfball is formed from a water resistant elastomer. In other embodiments,multi-layer balls are formed with at least a portion including the waterresistant elastomers of the invention. In this aspect of the invention,the intermediate layer, cover layer(s), and/or core may be formed, as awhole or in part, with the water resistant elastomeric composition.

The water resistant polyurethane elastomers of the invention are thereaction product of at least one isocyanate, at least one polyol and atleast one curing agent, wherein the polyol and/or the curing agent isbased on a hydrophobic backbone. The water resistant polyurea elastomeris the reaction product of at least one isocyanate and at least oneamine-terminated polyol, wherein the amine-terminated polyol and/or thecuring agent is based on a hydrophobic backbone.

The water resistant elastomers of the present invention may be used informing any portion of a golf ball, portions of golf clubs, shoes, orbags. When used in a golf ball, the water resistant elastomer preferablyis included in a layer composition from about 1 percent to about 100percent by weight of the layer composition.

In one embodiment, a golf ball of the invention includes a core and acover, wherein at least a portion of the golf ball is formed from awater resistant polyurea composition including an isocyanate, anamine-terminated compound comprising a hydrophobic backbone, and acuring agent. The amine-terminated compound may include at least one ofan unsaturated amine-terminated hydrocarbon, a saturatedamine-terminated hydrocarbon, or mixtures thereof. In addition, thecuring agent may be selected from the group consisting ofhydroxy-terminated curing agents, amine-terminated curing agents, andmixtures thereof. In another embodiment, the curing agent is selectedfrom the group consisting of primary diamine curing agents, secondarydiamine curing agents, triamines, and combinations thereof, preferably asecondary diamine curing agent. In this aspect of the invention, thegolf ball preferably has a weight gain of about 0.15 grams or less aftera seven week storage period in 100 percent humidity at 72° F. In oneembodiment, the golf ball has a weight gain of about 0.09 grams or lessafter a seven week storage period in 100 percent humidity at 72° F. Thewater resistant polyurea composition may also include at least onedensity-adjusting filler. And, in one embodiment, the water resistantpolyurea composition consists of only urea linkages.

In a second embodiment of this aspect of the invention, a golf ball mayinclude a core having a diameter of about 1.55 or greater, anintermediate layer disposed about the core to create a center, and acover having a thickness of about 0.02 inches to about 0.035 inchesdisposed about the center, wherein the cover includes a water resistantpolyurea material including at least one amine-terminated compoundcomprising a hydrophobic backbone and at least one isocyanate. In thisembodiment, the golf ball preferably has a weight gain of about 0.05grams or less after a seven week storage period in 100 percent humidityat 72° F.

In one embodiment, the amine-terminated compound includes at least oneamine-terminated hydrocarbon. In another embodiment, the cover has firsthardness and the intermediate layer has a second hardness greater thanthe first hardness. For example, the first hardness may be about 40Shore D to about 55 Shore D and the second hardness may be about 60Shore D or greater. Also, the core may include a first layer and asecond layer. In one embodiment, the core hardness is about 60 Shore Dor less.

In a third embodiment of this aspect of the invention, a golf ball mayinclude a water resistant polyurea composition including at least oneamine-terminated compound having at least one hydrophobic backbone,wherein the golf ball has a weight gain of about 0.15 grams or less anda size gain of about 0.001 inches or less after a seven week storageperiod in 100 percent humidity at 72° F. In one embodiment, the waterresistant polyurea composition further includes an isocyanate and acuring agent. In another embodiment, the curing is selected from thegroup consisting of ethylene diamine; hexamethylene diamine;1-methyl-2,6-cyclohexyl diamine; 2,2,4- and2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; 4,4′-dicyclohexylmethane diamine;1,4-cyclohexane-bis-(methylamine); 1,3-cyclohexane-bis-(methylamine);diethylene glycol bis-(aminopropyl)ether;2-methylpentamethylene-diamine; diaminocyclohexane; diethylene triamine;triethylene tetramine; tetraethylene pentamine; propylene diamine;1,3-diaminopropane; dimethylamino propylamine; diethylamino propylamine;imido-bis-(propylamine); monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; 4,4′-methylenebis-(2-chloroaniline);3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine;3,5-diethylthio-2,6-toluenediamine;4,4′-bis-(sec-butylamino)-diphenylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-benzene; 1,2-bis-(sec-butylamino)-benzene;N,N′-dialkylamino-diphenylmethane;trimethyleneglycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate;4,4′-methylenebis-(3-chloro-2,6-diethyleneaniline);4,4′-methylenebis-(2,6-diethylaniline); meta-phenylenediamine;paraphenylenediamine; N,N′-diisopropyl-isophoronediamine;polyoxypropylene diamine; propylene oxide-based triamine;3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof. Inthis aspect of the invention, the golf ball may have a polybutadienecore.

Golf balls of the invention may also be formed having at least a coverand at least one core layer, wherein at least one water resistantpolyurethane elastomer is included in the cover of the golf ball. Inanother embodiment, the golf ball has a cover, a core, and at least oneintermediate layer interposed between the cover and an outermost corelayer, wherein the intermediate layer is formed from a compositionincluding at least one water resistant polyurethane elastomer. In yetanother embodiment, the golf ball has a cover, a core, and at least oneintermediate layer interposed between the cover and the core, whereinthe outermost cover layer and at least one intermediate layer are bothformed from a composition including at least one water resistantpolyurethane elastomer.

The water resistant polyurethane elastomers used in forming the golfballs of the present invention can be formed in accordance with theteachings described in U.S. Pat. Nos. 5,334,673 and 5,733,428, which areincorporated by reference in their entirety herein.

The present invention is also directed to a golf ball including a coreand a cover, wherein at least a portion of the golf ball, e.g., a cover,is formed from a composition including an isocyanate, which may besaturated, and a block copolymer, wherein the block copolymer includesan A_(x)-B_(y)-A_(z) block and includes at least one functional group ata terminal end of the A_(x)-B_(y)-A_(z) block, and wherein x, y, and zare independently 1 or greater. In one embodiment, A includes an olefinand B includes a diene. In another embodiment, the diene is butadiene.The olefin may be selected from the group consisting of ethylene,propylene, styrene, and mixtures thereof.

In this aspect of the invention, the block copolymer may includestyrene-butadiene-styrene block copolymer. In one embodiment, the atleast one functional group includes a hydroxyl group, an amino group, athiol group, an epoxy group, an anhydride group, or a combinationthereof. The composition may include at least one density-adjustingfiller, nanoparticles, or a mixture thereof.

The present invention may also include a golf ball including a core anda cover, wherein at least a portion of the golf ball, e.g., a cover, isformed from an isocyanate and a block copolymer including at least onefunctional group at a terminal end of the block copolymer, wherein theblock copolymer includes an A_(x)-B_(y) block, and wherein x and y areindependently 1 or greater. In one embodiment, A includes an olefin andB includes a diene. In another embodiment, A includes styrene and Bincludes butadiene. Furthermore, the functional group can include atleast one of a hydroxy group, an amino group, a thiol group, an epoxygroup, an anhydride group, or a combination thereof.

In this aspect of the invention, the cover may include an inner coverlayer and an outer cover layer. And, in one embodiment, the inner coverlayer includes a thermoplastic material. Furthermore, the portion of thegolf ball may include the outer cover layer.

The present invention also relates to a golf ball including a core and acover, wherein the cover is formed from a composition including anisocyanate and a styrene-butadiene-styrene block copolymer havingfunctional groups at the terminal ends of the block copolymer. The golfball may also include an intermediate layer. In one embodiment, theintermediate layer includes a thermoplastic material. In anotherembodiment, the functional groups are selected from the group consistingof hydroxy groups, amino groups, thiol groups, epoxy groups, anhydridegroups, and combinations thereof. In still another embodiment, the coverhas an inner cover layer having a hardness of about 50 Shore D to about70 Shore D and an outer cover layer having a hardness of about 30 ShoreD to about 70 Shore D.

Another aspect of the invention relates to a golf ball including a coreand a cover, wherein the cover is formed from a polyurethane-basedcomposition including a prepolymer, a block copolymer, and a couplingagent, and wherein the prepolymer is formed from an isocyanate and apolyol. In one embodiment, the block copolymer includes anolefin-diene-olefin block. In another embodiment, the olefin is styreneand the diene is butadiene. In still another embodiment, the couplingagent includes a hydroxy group, an amino group, a thiol group, an epoxygroup, an anhydride group, or a combination thereof. For example, thecoupling agent may be selected from the group consisting oftrimethylolpropane monoallyl ether; N-methylolacrylamide;1,1-dihydroxymethylcyclohex-3-ene; 1,2-dihydroxymethylcyclohex-4-ene;1-amino-ethenol; 1-amino-2-propen-1-ol; 1-amino-1-propen-2-ol;1-amino-4-penten-2-ol; 1-amino-4-hexen-3-ol; 1-amino-3-penten-2-ol;1-amino-1-hepten-2-ol; 1-amino-3-nonen-2-ol; 2-amino-ethenol;2-amino-3-buten-1-ol; 2-amino-4-pentene-1-ol; 2-amino-5-hexen-1-ol;2-amino-3,14-octadecadien-1-ol; 2-amino-3,8-octadecadien-1-ol;2-amino-3,9-octadecadien-1-ol; 8-amino-1-octen-4-ol;4-amino-2-buten-2-ol; 4-amino-1-penten-3-ol; 4-amino-1,5-hexadiene-3-ol;4-amino-2,5-hexadiene-1-ol; ethynol; 4-amino-2-butyn-1-ol;1-amino-1-hydroxy-2-butenyl; 1-amino-3-pentyn-2-ol;1-amino-3-decyn-2-ol; and mixtures thereof. In yet another embodiment,the composition includes crosslinks. In the alternative, the compositioncan be thermoplastic.

The present invention is also directed to a golf ball including a coreand a cover, wherein the cover is formed from a polyurea compositionincluding a prepolymer, a block copolymer including at least onefunctional group at a terminal end, and a curative, wherein theprepolymer is formed from an isocyanate and a polyamine. The golf ballmay further include an intermediate layer disposed between the core andthe cover, which may be formed from, at least in part, a thermoplasticmaterial, e.g., an ionomer resin. In this aspect of the invention, theat least one functional group may be selected from the group consistingof a hydroxy group, an amino group, a thiol group, an epoxy group, ananhydride group, and combinations thereof. In one embodiment, the blockcopolymer includes an A_(x)-B_(y)-A_(z) block, wherein x, y, and z areindependently 1 or greater, and wherein A includes an olefin and Bincludes a diene. In another embodiment, the block copolymer includes anA_(x)-B_(y) block, wherein x and y are independently 1 or greater, andwherein A includes an olefin and B includes a diene.

The present invention also relates to a golf ball including a core and acover, wherein at least a portion of the golf ball is formed from apolyurea composition formed from a prepolymer, an olefin-diene-olefinblock copolymer, and a coupling agent. The golf ball may include anintermediate layer formed from a thermoplastic material. Furthermore,the coupling agent may be selected from the group consisting oftrimethylolpropane monoallyl ether; N-methylolacrylamide;1,1-dihydroxymethylcyclohex-3-ene; 1,2-dihydroxymethylcyclohex-4-ene;1-amino-ethenol; 1-amino-2-propen-1-ol; 1-amino-1-propen-2-ol;1-amino-4-penten-2-ol; 1-amino-4-hexen-3-ol; 1-amino-3-penten-2-ol;1-amino-1-hepten-2-ol; 1-amino-3-nonen-2-ol; 2-amino-ethenol;2-amino-3-buten-1-ol; 2-amino-4-pentene-1-ol; 2-amino-5-hexen-1-ol;2-amino-3,14-octadecadien-1-ol; 2-amino-3,8-octadecadien-1-ol;2-amino-3,9-octadecadien-1-ol; 8-amino-1-octen-4-ol;4-amino-2-buten-2-ol; 4-amino-1-penten-3-ol; 4-amino-1,5-hexadiene-3-ol;4-amino-2,5-hexadiene-1-ol; ethynol; 4-amino-2-butyn-1-ol;1-amino-1-hydroxy-2-butenyl; 1-amino-3-pentyn-2-ol;1-amino-3-decyn-2-ol; and mixtures thereof. In this aspect of theinvention, the block copolymer may include styrene-butadiene-styreneblock copolymer. Furthermore, the cover may have a thickness of about0.02 inches to about 0.035 inches. In one embodiment, the cover has aninner cover layer having a hardness of about 50 Shore D to about 70Shore D and an outer cover layer having a hardness of about 30 Shore Dto about 70 Shore D.

The present invention is also directed to a golf ball including a coreand a cover, wherein at least a portion of the golf ball is formed froma composition including a prepolymer and a curing agent, wherein theprepolymer is formed from a first prepolymer and a functionalized blockcopolymer, and wherein the prepolymer includes an A_(x)-B_(y)-A_(z)block capped by isocyanate end groups, wherein x, y, and z areindependently 1 or greater. In this aspect of the invention, thefunctionalized block copolymer may include at least one functional groupselected from the group consisting of hydroxy groups, amino groups,thiol groups, epoxy groups, anhydride groups, and combinations thereof.In one embodiment, the first prepolymer includes an isocyanate and apolyol. In an alternate embodiment, the first prepolymer includes anisocyanate and a polyamine. The curing agent may include ahydroxy-terminated curing agent, an amine-terminated curing agent, or amixture thereof.

In one embodiment, the A_(x)-B_(y)-A_(z) block includesolefin-diene-olefin. For example, the olefin-diene-olefin may bestyrene-butadiene-styrene. In another embodiment, the portion of thegolf ball formed from the composition of the invention has a moisturevapor transmission rate of about 0.01 to about 0.09 g/(m²×day) at 38° C.and 90 percent relative humidity.

The present invention further relates to a golf ball including a coreand a cover, wherein the cover is formed from a composition including aprepolymer and an amine-terminated curing agent, wherein the prepolymeris the reaction product of a first prepolymer and a functionalized blockcopolymer including an A_(x)-B_(y) block, wherein x and y areindependently 1 or greater, and wherein the first prepolymer includes anisocyanate and at least one of an amine-terminated component or ahydroxy-terminated component. In one embodiment, the prepolymer includesthe A_(x)-B_(y) block capped by isocyanate end groups. In anotherembodiment, the A_(x)-B_(y) block includes an olefin-diene block. Forexample, the A_(x)-B_(y) block may include a styrene-butadiene block. Inone embodiment, the cover includes an inner cover layer and an outercover layer, wherein the inner cover layer includes a thermoplasticmaterial, e.g., ionomer resin. In another embodiment, the functionalizedblock copolymer includes at least one functional group selected from thegroup consisting of hydroxy groups, amino groups, thiol groups, epoxygroups, anhydride groups, and combinations thereof.

The present invention is further directed to a golf ball including acore, an intermediate layer, and a cover, wherein the cover is formedfrom a composition including a prepolymer and a curing agent, whereinthe prepolymer includes a first prepolymer and a block copolymer havingfunctional groups at each terminal end, wherein the composition includesa hydrophobic A_(x)-B_(y) block or hydrophobic A_(x)-B_(y)-A_(z) blockcapped by isocyanate groups, and wherein x, y, and z are independently 1or greater. In one embodiment, the first prepolymer is formed from thereaction product of an isocyanate and an amine-terminated compound or ahydroxy-terminated compound. In an alternate embodiment, the firstprepolymer is the reaction product of an isocyanate and anamine-terminated compound.

In this aspect of the invention, the curing agent may be selected fromthe group consisting of ethylene diamine; hexamethylene diamine;1-methyl-2,6-cyclohexyl diamine; 2,2,4- and2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; 4,4′-dicyclohexylmethane diamine;1,4-cyclohexane-bis-(methylamine); 1,3-cyclohexane-bis-(methylamine);diethylene glycol bis-(aminopropyl) ether;2-methylpentamethylene-diamine; diaminocyclohexane; diethylene triamine;triethylene tetramine; tetraethylene pentamine; propylene diamine;1,3-diaminopropane; dimethylamino propylamine; diethylamino propylamine;imido-bis-propylamine; monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; 4,4′-methylenebis-(2-chloroaniline);3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine;3,5-diethylthio-2,6-toluenediamine;4,4′-bis-(sec-butylamino)-diphenylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-benzene; 1,2-bis-(sec-butylamino)-benzene;N,N′-dialkylamino-diphenylmethane;trimethyleneglycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate;4,4′-methylenebis-(3-chloro-2,6-diethyleneaniline);4,4′-methylenebis-(2,6-diethylaniline); meta-phenylenediamine;paraphenylenediamine; N,N′-diisopropyl-isophoronediamine;polyoxypropylene diamine; propylene oxide-based triamine;3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof.

In this aspect of the invention, the A_(x)-B_(y) block may include astyrene-butadiene block. Likewise, the A_(x)-B_(y)-A_(z) block mayinclude a styrene-butadiene-styrene block. In one embodiment, thefunctional groups are selected from the group consisting of hydroxygroups, amino groups, thiol groups, epoxy groups, anhydride groups, andcombinations thereof.

The present invention is also directed to a method for forming a golfball composition including the steps of:

-   -   forming a prepolymer including an isocyanate and at least one of        a hydroxy-terminated component or an amine-terminated component;    -   providing a block copolymer, wherein the block copolymer        includes at least one functional group at a terminal end of the        block copolymer;    -   reacting excess prepolymer with the block copolymer to form an        intermediate prepolymer;    -   chain extending the intermediate prepolymer with a curing agent        to form a composition including a hydrophobic block capped by        isocyanate groups.        In one embodiment, the hydrophobic block includes an A_(x)-B_(y)        block, wherein x and y are independently 1 or greater, and        wherein A includes an olefin and B includes a diene. In an        alternate embodiment, the hydrophobic block includes an        A_(x)-B_(y)-A_(z) block, wherein x and y are independently 1 or        greater, and wherein A includes an olefin and B includes a        diene. For example, the olefin may include styrene and the diene        may include butadiene. In addition, the step of forming the        prepolymer may include forming the reaction product of an        isocyanate and an amine-terminated component. The curing agent        may be an amine-terminated curing agent.

In this aspect of the invention, the step of providing a block copolymermay further include the steps of:

-   -   providing a block copolymer including an A_(x)-B_(y) block or        A_(x)-B_(y)-A_(z) block, wherein x, y, and z are independently 1        or greater;    -   providing a coupling agent including at least one hydroxy group,        amino group, thiol group, epoxy group, anhydride group, or        mixture thereof;    -   functionalizing the block copolymer with the coupling agent to        provide a functionalized block copolymer.        The present invention further relates to a method for forming a        golf ball component including the steps of:    -   forming a prepolymer including an isocyanate and at least one of        a hydroxy-terminated component or an amine-terminated component;    -   providing a block copolymer including an A_(x)-B_(y) block or an        A_(x)-B_(y)-A_(z) block, wherein x, y, and z are independently 1        or greater, and wherein the block copolymer includes at least        one functional group at a terminal end of the block copolymer;    -   reacting the prepolymer with the block copolymer to form the        composition;    -   forming the composition into a golf ball component.        In one embodiment, the A_(x)-B_(y) block includes an        olefin-diene block. For example, the olefin-diene block may be        styrene-butadiene. In an alternate embodiment, the        A_(x)-B_(y)-A_(z) block includes an olefin-diene-olefin block,        e.g., styrene-butadiene-styrene.

In this aspect of the invention, the step of providing a block copolymermay further include the steps of:

-   -   providing a coupling agent including at least one hydroxy group,        amino group, thiol group, epoxy group, anhydride group, or        mixture thereof;    -   functionalizing the block copolymer with the coupling agent to        provide a functionalized block copolymer.        In one embodiment, the step of forming a golf ball component        includes providing a core and forming the composition about the        core. In addition, the step of forming the composition about the        core may further include casting the composition.

BRIEF DESCRIPTION OF THE DRAWINGS

Further features and advantages of the invention can be ascertained fromthe following detailed description that is provided in connection withthe drawing(s) described below:

FIG. 1 is a cross-sectional view of a two-piece golf ball, wherein thecover is formed from a composition of the invention;

FIG. 2 is a cross-sectional view of a multi-component golf ball, whereinat least the cover is formed from a composition of the invention;

FIG. 3 is a cross-sectional view of a multi-component golf ball, whereinthe cover is formed from a composition of the invention and theintermediate layer is formed from a composition including athermoplastic material;

FIG. 4 is a cross-sectional view of a multi-component golf ballincluding a core and a cover, wherein the core is surrounded by atensioned elastomeric material and the cover is formed from acomposition of the invention;

FIG. 5 is a cross-sectional view of a liquid center golf ball whereinthe liquid core is surrounded by a tensioned elastomeric material andthe cover is formed from a composition of the invention;

FIG. 6 is a cross-sectional view of a multi-component golf ballincluding a core, a thin inner cover layer, and a thin outer cover layerdisposed thereon, wherein the cover is formed from a composition of theinvention;

FIG. 7 is a cross-sectional view of a multi-component golf ballincluding a core, an outer core layer, a thin inner cover layer, and athin outer cover layer disposed thereon, wherein the cover is formedfrom a composition of the invention;

FIG. 8 is a cross-sectional view of a multi-component golf ballincluding a large core and a thin outer cover layer disposed thereon,wherein the cover is formed from a composition of the invention;

FIG. 9 is a graphical representation of the weight changes of golf ballssubjected to controlled temperature and humidity over a specified amountof time; and

FIG. 10 is a graphical representation of the size changes of golf ballssubjected to controlled temperature and humidity over a specified amountof time.

DETAILED DESCRIPTION OF THE INVENTION

The present invention contemplates improved light stable and moistureresistant compositions for use in golf equipment, such as golf balls,golf clubs, or the like. In particular, the compositions of theinvention preferably include polyurethane-based block copolymers,polyurea-based block copolymers, or mixtures thereof and are included ina variety of golf ball constructions, i.e., one-piece, two-piece, ormultilayer balls, as well as golf club components, e.g., club headinserts.

The enhanced light stability of the compositions of the inventionenables the production of various golf equipment components withphysical and aerodynamic properties better than or equal to golf ballsincorporating polyurea or polyurethane compositions without light stableblends.

Light stability may be accomplished in a variety of ways for thepurposes of this application. For example, the compositions of theinvention may include only saturated components, i.e., componentssubstantially free of unsaturated carbon-carbon bonds or aromaticgroups. The term “saturated,” as used herein, refers to compositionshaving saturated aliphatic and alicyclic polymer backbones, i.e., withno carbon-carbon double bonds. The compositions of the invention mayalso include a light stabilizer to improve light stability when usingaromatic components and are preferably saturated. In addition, the useof a composition including a hydrogenated block copolymer enhances thelight stability of the compositions. In particular, the use ofhydrogenated styrene-butadiene-styrene results in enhanced lightstability due to the fact that adding hydrogen causes the double bond tobecome a single bond.

Furthermore, because conventional polyurethane and polyurea elastomersare prone to absorption of moisture, the present invention providesnovel compositions to improve the water resistance of golf equipmentcompositions. For example, the polyurethane-based and polyurea-basedblock copolymers of the present invention provide hydrophobicity, inaddition to resiliency and durability. In addition, when the elastomersof the invention are based on hydrophobic backbones, the improvedmoisture resistance of these compositions result in golf equipment withimproved stability with respect to its resistance to the absorption ofmoisture.

Thus, the improved performance characteristics of the golf equipment ofthe present invention demonstrate a distinct benefit to the golfer byproviding golf equipment that exhibits consistent behavior over a widerange of environmental conditions.

Polyurea-Based Compositions

Polyurea-based compositions, which are distinctly different frompolyurethane-based compositions, result in desirable aerodynamic andaesthetic characteristics when used in golf equipment and ballcomponents. Conventional aromatic polyurethane/urethane elastomers andpolyurethane/urea elastomers are generally prepared by curing aprepolymer of diisocyanate and polyol with at least one diol curingagent or at least one diamine curing agent, respectively. Without beingbound to any particular theory, it is now believed that substitution ofthe long chain polyol segment in the polyurethane prepolymer with a longchain amine-terminated compound to form a polyurea prepolymer, improvesshear, cut, and resiliency, as well as adhesion to other components.

As mentioned above, the polyurea-based compositions of the inventionprovide improved moisture resistance and light stability. Thepolyurea-based compositions of this invention may be formed in severalways: a) from the reaction product of an isocyanate and amine-terminatedcompound prepolymer crosslinked with a curing agent; b) from thereaction product of an isocyanate and an amine-functionalized blockcopolymer; c) from the reaction product of a polyurea-based prepolymerand an amine-functionalized block copolymer; and d) by reacting anexcess of a polyurea-based prepolymer and an amine-terminated blockcopolymer to form an intermediate prepolymer having the block copolymercapped at each end with isocyanate groups, which is cured with a curingagent.

For example, polyurea-based compositions of the invention may beprepared from at least one isocyanate, at least one amine-terminatedcompound based on a hydrophobic backbone, and at least one diol curingagent or at least one diamine curing agent, preferably a secondarydiamine curing agent. The hydrophobic backbone provides increased waterresistance. In another aspect, the compositions of the invention includethe reaction product of an isocyanate and an amine-functionalized blockcopolymer, wherein the isocyanate is coupled with the block copolymer atthe terminal end. The presence of the rubbery mid-section in the blockcopolymer, or a hydrogenated moiety, provides both flexibility andhydrophobicity to the composition.

The polyurea-based compositions of the invention may be formed of onlysaturated components, which have greater light stability, or may includeone or more unsaturated components and a light stabilizer. In addition,when the compositions of the invention are formed using a hydrogenatedblock copolymer, such as hydrogenated styrene-butadiene-styrene, addinghydrogen causes the double bond to become a single bond, which enhancesthe light stability.

Compositions of the Invention

The compositions of the invention may be formed in several ways. Forexample, the compositions may be formed from the reaction product of anisocyanate and a functionalized block copolymer. When forming apolyurethane-based composition, the functional groups of the blockcopolymer are amine groups, whereas the functional groups are hydroxygroups when forming a polyurethane-based composition. In addition, thecompositions of the present invention may be formed from the reactionproduct of a prepolymer, which is based on an isocyanate and a polyol oramine, and a functionalized block copolymer. The compositions of theinvention may also be formed by reacting an excess of prepolymer, whichis based on an isocyanate and a polyol or amine, with a functionalizedblock copolymer to form an intermediate prepolymer having the blockcopolymer portion capped with isocyanate groups at each end, which isthen reacted with a curing agent to form a polyurethane-based orpolyurea-based composition. Finally, the compositions of the inventionmay be formed by curing a polyurethane or polyurea prepolymer with anamine-terminated or hydroxy-terminated curing agent.

Such novel compositions are advantageous in that the beneficialproperties of the separate polymers are accentuated, while thedetrimental qualities are compensated for, or completely overcome. Forexample, a conventional polyurea or polyurethane composition is moisturesensitive and is not compatible with non-polar polymer layers, but has agood low temperature and scuff resistance. On the other hand,conventional block copolymers, such as styrene-butadiene-styrene (SBS)block copolymers, or their hydrogenated derivatives, are hydrophobic,but lack resiliency, are not compatible with polar polymers, and causesevere delamination when used in golf ball layers. As such, coupling thepolyurea prepolymer or polyurethane prepolymer with an SBS blockcopolymer provides the hydrophobicity of the SBS block copolymer and thescuff resistance of the prepolymer.

In addition, when a polyurea-block SBS, polyurethane-block SBS, orderivative thereof, is used in golf equipment according to theinvention, there are several advantages over golf equipment formed fromconventional compositions. For example, golf ball components formed froma polyurea-block SBS or a polyurethane-block SBS have improved scuffresistance and resiliency over golf ball components formed fromconventional SBS block copolymers due to the urea/urethane moiety.Furthermore, the urea and urethane moieties allow blending with otherpolar polymers such as polycarbonate, polyester, polyamide, acidcopolymers, ionomers, and the like. Also, the presence of diene/olefinichydrocarbon moiety enables blending with non-polar polymers such aspolyethylene, polypropylene, polystyrene, and the like. As such, theadhesion to other polar and non-polar layers is improved over golf ballcomponents formed from conventional compositions. Moreover, the presenceof the butadiene moiety, or hydrogenated moiety, provides flexibilityand hydrophobicity to the golf ball component.

Reacting an Isocyanate and a Functionalized Block Copolymer

The compositions of the invention may be formed by coupling anisocyanate with a block copolymer. In particular, block copolymers canbe functionalized at the terminal end with a hydroxy group or aminegroup and then reacted with an isocyanate to form a polyurea-basedpolymer or a polyurethane-based polymer.

Suitable block copolymers for use with the present invention include,but are not limited to, block copolymers having a general A_(x)B_(y)block or an A_(x)B_(y)A_(z) block, where x, y, and z represent the chainlengths and are independently 1 or greater. For example, x can be 2, ycan be 1, and z can be 2. However, each chain length can be the same ordifferent.

The block copolymer may be an olefin-diene (A-B) block copolymer, suchas styrene-butadiene block copolymer, ethylene-butadiene blockcopolymer, and propylene butadiene block copolymer. In addition, theblock copolymer may be an olefin-diene-olefin (A-B-A) block copolymer,such as styrene-butadiene-styrene block copolymer (SBS block copolymer),hydrogenated SBS block copolymer, ethylene-butadiene-ethylene blockcopolymer, and propylene-butadiene-propylene block copolymer. In analternative embodiment, the block copolymers of the invention may beacrylic-based, for example, the A in the AB or ABA block may beacrylate.

Those of ordinary skill in the art should be well aware of the generalcharacteristics of block copolymers and the methods for making them. Forexample, SBS block copolymer is made up of three segments, i.e., two endchains of polystyrene and a middle long chain of polybutadiene, and hasthe following general structure:

where n is the length of the chain, i.e., 1 or greater. Becausepolystyrene is a hard plastic, the SBS block copolymer is durable. And,SBS block copolymer has elastomeric properties without beingcrosslinked, which is different from most rubbers. In addition, thepolystyrene chains have a tendency to cluster together so that when onepolystyrene group of an SBS molecule joins a cluster, and the otherpolystyrene group on the same SBS molecule joins another cluster, thedifferent clusters become coupled together with the elasticpolybutadiene chains. This gives the SBS block copolymer the ability toretain its shape after being stretched.

Living anionic polymerization, i.e., polymerization without anytermination reactions, may be used to make the SBS block copolymers ofthe invention. The general polymerization process is as follows:

where n is the chain length, i.e., 1 or greater, and wherein R is abutyl group.

Because the SBS block copolymer, or hydrogenated SBS, does not havefunctional groups, a coupling agent is needed to functionalize the blockcopolymer so that it can be reacted with the isocyanate. The couplingagent may be based on the following general structure:R—R₁—Rwhere R₁ is any alkyl group including single bonds, double bonds, triplebonds, or a combination thereof and where the terminal groups (R) may behydroxy groups, amino groups, thiol groups, epoxy groups, anhydridegroups, or mixtures thereof. In one embodiment, R₁ has about 1 to about36 carbon atoms, preferably about 1 to about 20 carbons atoms, and morepreferably about 1 to about 18 carbon atoms.

Suitable hydroxy-terminated compounds that may be used as couplingagents according to the invention include, but are not limited to, thefollowing:

As generally addressed above, the coupling agent can also be monoamineand mono-hydroxy-terminated compounds with the following generalstructure:H₂N—R₁—OHwhere R₁ can be any alkyl group. In one embodiment, R₁ has about 1 toabout 20 carbon atoms, preferably about 2 to about 20 carbons atoms.

Examples of coupling agents suitable for use with the present inventioninclude, but are not limited to, 1-amino-ethenol; 1-amino-2-propen-1-ol;1-amino-1-propen-2-ol; 1-amino-4-penten-2-ol; 1-amino-4-hexen-3-ol;1-amino-3-penten-2-ol; 1-amino-1-hepten-2-ol; 1-amino-3-nonen-2-ol;2-amino-ethenol; 2-amino-3-buten-1-ol; 2-amino-4-pentene-1-ol;2-amino-5-hexen-1-ol; 2-amino-3,14-octadecadien-1-ol;2-amino-3,8-octadecadien-1-ol; 2-amino-3,9-octadecadien-1-ol;8-amino-1-octen-4-ol; 4-amino-2-buten-2-ol; 4-amino-1-penten-3-ol;4-amino-1,5-hexadiene-3-ol; 4-amino-2,5-hexadiene-1-ol; ethynol;4-amino-2-butyn-1-ol; 1-amino-1-hydroxy-2-butenyl;1-amino-3-pentyn-2-ol; 1-amino-3-decyn-2-ol; and mixtures thereof.

The alkyl group in the coupling agent may contain single bonds, doublebonds, or triple bonds. In one embodiment, the alkyl group includessingle bonds and double bonds. In another embodiment, the alkyl groupincludes only single bonds. For example, saturated coupling agentssuitable for use with the present invention include, but are not limitedto, 1-amino-ethanol, 2-amino-propan-1-ol, 2-amino-butan-4-ol,3-amino-hexan-4-ol; 4-amino-pentan-1-ol, and mixtures thereof.

Reacting a Prepolymer and a Functionalized Block Copolymer

In another aspect of the invention, the compositions of the inventionmay be formed by reacting a polyurethane or polyurea prepolymer with afunctionalized block copolymer. The functionalized block copolymer maybe any of the block copolymers discussed above. The mechanism for thereaction is similar to above in that the functional groups of the blockcopolymer (obtained by using a coupling agent with the block copolymer)react with the NCO groups of the isocyanate in the prepolymer.

As briefly mentioned above, the prepolymer used in this aspect of theinvention may be a polyurethane prepolymer or a polyurea prepolymer. Thepolyurea prepolymer is the reaction product of an amine-terminatedcomponent and an isocyanate, whereas the polyurethane prepolymer is thereaction product of a hydroxy-terminated component and an isocyanate.The particular components of the prepolymers will be discussed ingreater detail below.

Because the main difference between the polyurea prepolymer and thepolyurethane prepolymer is the amine-terminated component/polyolcomponent, the isocyanates discussed are intended to be used in eithertype of prepolymer.

Any isocyanate available to one of ordinary skill in the art is suitablefor use in the prepolymers according to the invention. Isocyanates foruse with the present invention include aliphatic, cycloaliphatic,aromatic aliphatic, aromatic, any derivatives thereof, and combinationsof these compounds having two or more isocyanate (NCO) groups permolecule. As used herein, aromatic aliphatic compounds should beunderstood as those containing an aromatic ring, wherein the isocyanategroup is not directly bonded to the ring. One example of an aromaticaliphatic compound is a tetramethylene diisocyanate (TMXDI).

The isocyanates may be organic polyisocyanate-terminated prepolymers,low free isocyanate prepolymer, and mixtures thereof. Theisocyanate-containing reactable component may also include anyisocyanate-functional monomer, dimer, trimer, or polymeric adductthereof, prepolymer, quasi-prepolymer, or mixtures thereof.Isocyanate-functional compounds may include monoisocyanates orpolyisocyanates that include any isocyanate functionality of two ormore.

Suitable isocyanate-containing components include diisocyanates havingthe generic structure: O═C═N—R—N═C═O, where R is preferably a cyclic,aromatic, or linear or branched hydrocarbon moiety containing from about1 to about 20 carbon atoms. The isocyanate may also contain one or morecyclic groups or one or more phenyl groups. When multiple cyclic oraromatic groups are present, linear and/or branched hydrocarbonscontaining from about 1 to about 10 carbon atoms can be present asspacers between the cyclic or aromatic groups. In some cases, the cyclicor aromatic group(s) may be substituted at the 2-, 3-, and/or4-positions, or at the ortho-, meta-, and/or para-positions,respectively. Substituted groups may include, but are not limited to,halogens, primary, secondary, or tertiary hydrocarbon groups, or amixture thereof.

Examples of isocyanates that can be used with the present inventioninclude, but are not limited to, substituted and isomeric mixturesincluding 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI);3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI); toluene diisocyanate(TDI); polymeric MDI; carbodiimide-modified liquid 4,4′-diphenylmethanediisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylenediisocyanate (MPDI); triphenyl methane-4,4′- and triphenylmethane-4,4″-triisocyanate; naphthylene-1,5-diisocyanate; 2,4′-, 4,4′-,and 2,2-biphenyl diisocyanate; polyphenylene polymethylenepolyisocyanate (PMDI) (also known as polymeric PMDI); mixtures of MDIand PMDI; mixtures of PMDI and TDI; ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene-1,2-diisocyanate;tetramethylene-1,3-diisocyanate; tetramethylene-1,4-diisocyanate;1,6-hexamethylene diisocyanate (HDI); octamethylene diisocyanate;decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate;2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate;dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; methylcyclohexylene diisocyanate (HTDI);2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate;4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate;1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl)dicyclohexane;2,4′-bis(isocyanatomethyl)dicyclohexane; isophorone diisocyanate (IPDI);triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexanediisocyanate (TMDI); 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI);2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate;1,2-, 1,3-, and 1,4-phenylene diisocyanate; aromatic aliphaticisocyanate, such as 1,2-, 1,3-, and 1,4-xylene diisocyanate;meta-tetramethylxylene diisocyanate (m-TMXDI); para-tetramethylxylenediisocyanate (p-TMXDI); trimerized isocyanurate of any polyisocyanate,such as isocyanurate of toluene diisocyanate, trimer of diphenylmethanediisocyanate, trimer of tetramethylxylene diisocyanate, isocyanurate ofhexamethylene diisocyanate, and mixtures thereof; dimerized uretdione ofany polyisocyanate, such as uretdione of toluene diisocyanate, uretdioneof hexamethylene diisocyanate, and mixtures thereof; modifiedpolyisocyanate derived from the above isocyanates and polyisocyanates;and mixtures thereof.

When forming a saturated composition, the following saturatedisocyanates are preferably used: ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate (HDI);octamethylene diisocyanate; decamethylene diisocyanate;2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylenediisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethanediisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; methylcyclohexylene diisocyanate (HTDI);2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate;4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate;1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl)dicyclohexane;2,4′-bis(isocyanatomethyl)dicyclohexane; isophorone diisocyanate (IPDI);triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexanediisocyanate (TMDI); 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI);2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate;and mixtures thereof. Aromatic aliphatic isocyanates may also be used toform light stable materials. Examples of such isocyanates include 1,2-,1,3-, and 1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate(m-TMXDI); para-tetramethylxylene diisocyanate (p-TMXDI); trimerizedisocyanurate of any polyisocyanate, such as isocyanurate of toluenediisocyanate, trimer of diphenylmethane diisocyanate, trimer oftetramethylxylene diisocyanate, isocyanurate of hexamethylenediisocyanate, and mixtures thereof; dimerized uretdione of anypolyisocyanate, such as uretdione of toluene diisocyanate, uretdione ofhexamethylene diisocyanate, and mixtures thereof; a modifiedpolyisocyanate derived from the above isocyanates and polyisocyanates;and mixtures thereof. In addition, the aromatic aliphatic isocyanatesmay be mixed with any of the saturated isocyanates listed above for thepurposes of this invention.

The number of unreacted NCO groups in the polyurea-based composition maybe varied to control such factors as the speed of the reaction, theresultant hardness of the composition, and the like. For example, as theweight percent of unreacted isocyanate groups increases, the hardnessalso increases in a somewhat linear fashion. Thus, when the NCO contentis about 10.5 weight percent, the hardness may be less than about 55Shore A, whereas once the NCO content increases about 15 weight percent,the hardness is greater than about 80 Shore A.

In one embodiment, the number of unreacted NCO groups in thepolyurea-based composition may be less than about 14 percent. In oneembodiment, the polyurea-based composition has from about 5 percent toabout 11 percent unreacted NCO groups, and even more preferably has fromabout 6 to about 9.5 percent unreacted NCO groups. In one embodiment,the percentage of unreacted NCO groups is about 3 percent to about 9percent. Alternatively, the percentage of unreacted NCO groups may beabout 7.5 percent or less, and more preferably, about 7 percent or less.In another embodiment, the unreacted NCO content is from about 2.5percent to about 7.5 percent, and more preferably from about 4 percentto about 6.5 percent.

When formed, the prepolymers may contain about 10 percent to about 20percent by weight of the prepolymer of free isocyanate monomer. Thus, inone embodiment, the prepolymer may be stripped of the free isocyanatemonomer. For example, after stripping, the prepolymer may contain about1 percent or less free isocyanate monomer. In another embodiment, theprepolymer contains about 0.5 percent by weight or less of freeisocyanate monomer.

Any amine-terminated compound available to one of ordinary skill in theart is suitable for use in the polyurea prepolymer. The amine-terminatedcompound may include amine-terminated hydrocarbons, amine-terminatedpolyethers, amine-terminated polyesters, amine-terminatedpolycarbonates, amine-terminated polycaprolactones, and mixturesthereof. The amine-terminated segments may be in the form of a primaryamine (NH₂) or a secondary amine (NHR).

The molecular weight of the amine-terminated compound for use in theinvention may range from about 100 to about 10,000. As used herein, theterm “about” is used in connection with one or more numbers or numericalranges, should be understood to refer to all such numbers, including allnumbers in a range. In one embodiment, the amine-terminated compound isabout 500 or greater, preferably about 1000 or greater, and even morepreferably about 2000 or greater. In another embodiment, theamine-terminated compound molecular weight is about 8000 or less,preferably about 4,000 or less, and more preferably about 3,000 or less.For example, in one embodiment, the molecular weight of theamine-terminated compound is about 1000 to about 4000. Because lowermolecular weight polyether amines may be prone to forming solidpolyureas, a higher molecular weight oligomer may be used to avoid solidformation.

In one embodiment, the amine-terminated compound includesamine-terminated hydrocarbons having the following generic structures:

where x is the chain length, i.e., 1 or greater, n is preferably about 1to about 12, and R is any alkyl group having from about 1 to about 20carbon atoms, preferably about 1 to about 12 carbon atoms, a phenylgroup, a cyclic group, or mixture thereof.

The amine-terminated compound may also includes amine-terminatedpolyethers having following generic structures:

where x is the chain length, i.e., 1 or greater, n is preferably about 1to about 12, and R is any alkyl group having from about 1 to about 20carbon atoms, preferably about 1 to about 12 carbon atoms, a phenylgroup, a cyclic group, or mixture thereof. One example of anamine-terminated polyether is a polyether amine. As used herein,“polyether amine” refers to a polyoxyalkyleneamine containing primaryamino groups attached to the terminus of a polyether backbone. Due tothe rapid reaction of isocyanate and amine, and the insolubility of manyurea products, however, the selection of diamines and polyether aminesis limited to those allowing the successful formation of the polyureaprepolymers. In one embodiment, the polyether backbone is based ontetramethylene, propylene, ethylene, trimethylolpropane, glycerin, andmixtures thereof.

In one embodiment, the polyether amine has the generic structure:

wherein the repeating unit x has a value ranging from about 1 to about70, R is any alkyl group having from about 1 to about 20 carbon atoms,preferably about 1 to about 12 carbon atoms, a phenyl group, a cyclicgroup, or mixture thereof, and R₃ is a hydrogen, methyl group, or amixture thereof. Even more preferably, the repeating unit may be fromabout 5 to about 50, and even more preferably is from about 12 to about35.

In another embodiment, the polyether amine has the generic structure:

wherein the repeating units x and z have combined values from about 3.6to about 8 and the repeating unit y has a value ranging from about 9 toabout 50, R is an alkyl group having about 1 to about 20 carbons, aphenyl group, a cyclic group, or mixtures thereof, R₁ is —(CH₂)_(a)—,wherein “a” may be a repeating unit ranging from about 1 to about 10, aphenylene group, a cyclic group, or mixtures thereof, and R₃ is ahydrogen, methyl group, or a mixture thereof.

In yet another embodiment, the polyether amine has the genericstructure:H₂N—(R₁)—O—(R₁)—O—(R₁)—NH₂;H₂N—(R₁)—O—(R₁)—O—(R₁)—NHR; orRHN—(R₁)—O—(R₁)—O—(R₁)—NHRwherein R is an alkyl group having about 1 to about 20 carbons, phenylgroups, cyclic groups, or mixtures thereof, and wherein R₁ is—(CH2)_(a)—, wherein “a” may be a repeating unit ranging from about 1 toabout 10, a phenylene group, a cyclic group, or mixtures thereof.

Suitable polyether amines include, but are not limited to,methyldiethanolamine; polyoxyalkylenediamines such as,polytetramethylene ether diamines, polyoxypropylenetriamine,polyoxyethylene diamines, and polyoxypropylene diamines; poly(ethyleneoxide capped oxypropylene) ether diamines; propylene oxide-basedtriamines; triethyleneglycoldiamines; trimethylolpropane-basedtriamines; glycerin-based triamines; and mixtures thereof. In oneembodiment, the polyether amine used to form the prepolymer isJeffamine® D2000 (manufactured by Huntsman Corporation of Austin, Tex.).

The molecular weight of the polyether amine for use in the invention mayrange from about 100 to about 5000. In one embodiment, the polyetheramine molecular weight is about 200 or greater, preferably about 230 orgreater. In another embodiment, the molecular weight of the polyetheramine is about 4000 or less. In yet another embodiment, the molecularweight of the polyether amine is about 600 or greater. In still anotherembodiment, the molecular weight of the polyether amine is about 3000 orless. In yet another embodiment, the molecular weight of the polyetheramine is between about 1000 and about 4000, preferably about 1000 toabout 4000, and more preferably is between about 1500 to about 2500.Because lower molecular weight polyether amines may be prone to formingsolid polyureas during prepolymer preparation, a higher molecular weightoligomer, such as Jeffamine®V D2000, is preferred.

In addition, the amine-terminated compound may include amine-terminatedpolyesters having the generic structures:

where x is the chain length, i.e., 1 or greater, preferably about 1 toabout 20, R is any alkyl group having from about 1 to about 20 carbonatoms, preferably about 1 to about 12 carbon atoms, a phenyl group, acyclic group, or mixture thereof, and R₁ and R₂ are straight or branchedhydrocarbon chains, e.g., alkyl or aryl chains.

Copolymers of polycaprolactone and polyamines may also be used to formthe polyurea prepolymers of the present invention. These copolymersinclude, but are not limited to, bis(2-aminoethyl)ether initiatedpolycaprolactone, 2-(2-aminoethylamino)ethanol,2-2(aminoethylamino)ethanol, polyoxyethylene diamine initiatedpolycaprolactone, propylene diamine initiated polycaprolactone,polyoxypropylene diamine initiated polycaprolactone, 1,4-butanediamineinitiated polycaprolactone, trimethylolpropane-based triamine initiatedpolycaprolactone, neopentyl diamine initiated polycaprolactone,hexanediamine initiated polycaprolactone, polytetramethylene etherdiamine initiated polycaprolactone, and mixtures thereof. In addition,polycaprolactone polyamines having the following structures may beuseful in forming the polyurea prepolymers of the present invention:

where x is the chain length, i.e., 1 or greater, preferably about 1 toabout 20, R is one of an alkyl group having from about 1 to about 20carbons, preferably about 1 to about 12 carbons, a phenyl group, or acyclic group, and R₁ is a straight or branched hydrocarbon chainincluding about 1 to about 20 carbons.

where x is the chain length, i.e., 1 or greater, preferably about 1 toabout 20, R is one of an alkyl group having from about 1 to about 20carbons, preferably about 1 to about 12 carbons, a phenyl group, or acyclic group, and R₁ is a straight or branched hydrocarbon chainincluding about 1 to about 20 carbons.

In another embodiment, the amine-terminated compound may be anamine-terminated polycarbonate having one of the following genericstructures:

where x is the chain length, which preferably ranges from about 1 toabout 20, R is one of an alkyl group having from about 1 to about 20carbons, preferably about 1 to about 12 carbons, a phenyl group, or acyclic group, and R₁ is a straight chain hydrocarbon or predominantlybisphenol A units or derivatives thereof.

Amine-terminated polyamides may also be reacted with the isocyanatecomponent to form the polyurea prepolymer component of the presentinvention. Suitable amine-terminated polyamides include, but are notlimited to, those having following structures:

where x is the chain length, i.e., about 1 or greater, R is one of analkyl group having from about 1 to about 20 carbons, preferably about 1to about 12 carbons, a phenyl group, or a cyclic group, R₁ is an alkylgroup having about 1 to about 12 carbon atoms, a phenyl group, or acyclic group, and R₂ is an alkyl group having about 1 to about 12 carbonatoms (straight or branched), a phenyl group, or a cyclic group.

Additional amine-terminated compounds may also be useful in forming thepolyurea prepolymers of the present invention include, but are notlimited to, poly(acrylonitrile-co-butadiene); poly(1,4-butanediol)bis(4-aminobenzoate) in liquid or waxy solid form; linear and branchedpolyethylenimine; low and high molecular weight polyethylenimine havingan average molecular weight of about 500 to about 30,000; poly(propyleneglycol) bis(2-aminopropyl ether) having an average molecular weight ofabout 200 to about 5,000; polytetrahydrofuran bis(3-aminopropyl)terminated having an average molecular weight of about 200 to about2000; and mixtures thereof, all of which are available from Aldrich ofMilwaukee, Wis.

Thus, in one embodiment, the polyurea prepolymer includes apoly(acrylonitrile-co-butadiene) having one of the following structures:

wherein x and y are chain lengths, i.e., greater than about 1, R is anyalkyl group having from about 1 to about 20 carbon atoms, preferablyabout 1 to about 12 carbon atoms, a phenyl group, a cyclic group, ormixture thereof, R₁ is a hydrogen, methyl group, cyano group, phenylgroup, or a mixture thereof, and R₂ is a hydrogen, a methyl group,chloride, or a mixture thereof. In one embodiment, the y:x ratio isabout 82:18 to about 90:10. In other words, thepoly(acrylonitrile-co-butadiene) may have from about 10 percent to about18 percent acrylonitrile by weight.

In another embodiment, the polyurea prepolymer includes apoly(1,4-butanediol) bis(4-aminobenzoate) having one of the followingstructures:

where x and n are chain lengths, i.e., 1 or greater, and n is preferablyabout 1 to about 12, R and R₁ are linear or branched hydrocarbon chains,an alkyl group having from about 1 to about 20 carbons, preferably about1 to about 12 carbons, a phenyl group, a cyclic group, or mixturesthereof, and R₂ is a hydrogen, a methyl group, or a mixture thereof. Inone embodiment, R₁ is phenyl, R₂ is hydrogen, and n is about 2.

In yet another embodiment, the polyurea prepolymer includes at least onelinear or branched polyethyleneimine having one of the followingstructures:

wherein x and y are chain lengths, i.e., greater than about 1, R is anyalkyl group having from about 1 to about 20 carbon atoms, preferablyabout 1 to about 12 carbon atoms, a phenyl group, a cyclic group, ormixture thereof, and R₁ is a hydrogen, methyl group, or a mixturethereof. In one embodiment, R₁ is hydrogen. In another embodiment, thepolyurea prepolymer includes a mixture of linear and branchedpolyethyleneimines.

In still another embodiment, the polyurea prepolymer of the presentinvention includes a polytetrahydrofuran bis(3-aminopropyl) terminatedcompound having one of the following structures:

where m and n are chain lengths, i.e., 1 or greater, n is preferablyabout 1 to about 12 and m is preferably about 1 to about 6, R is any onealkyl group having from about 1 to about 20 carbons, preferably about 1to about 12 carbons, a phenyl group, a cyclic group, or mixturesthereof, and R₁ and R₂ are hydrogen, methyl groups, or mixtures thereof.In one embodiment, both R₁ and R₂ are hydrogen and both m and n areabout 2.

In addition, diamines and triamines may be used with an isocyanate toform the polyurea prepolymer of the present invention. In oneembodiment, aromatic diamines may be used when an ultraviolet stabilizeror whitening agent is intended to be incorporated during postprocessing.U.S. Pat. No. 5,484,870 provides suitable aromatic diamines suitable foruse with the present invention, the entire disclosure of which isincorporated by reference herein. For example, useful aromaticpolyamines include polymethylene-di-p-aminobenzoates,polyethyleneglycol-bis(4-aminobenzoate), polytetramethyleneetherglycol-di-p-aminobenzoate, polypropyleneglycol-di-p-aminobenzoate,and mixtures thereof. In addition, triamines that may be used in formingthe prepolymer of the invention includeN,N,N′,N′-tetramethyl-ethylenediamine, 1,4-diazobicyclo(2,2,2)-octane,N-methyl-N′-dimethylaminoethylpiperazine, N,N-dimethylbenzylamine,bis-(N,N-diethylaminoethyl)-adipate, N,N-diethylbenzylamine,pentamethyldiethylenetriamine, N,N-dimethylclyclohexylamine,N,N,N′,N′-tetramethyl-1,3-butanediamine,N,N-dimethyl-beta-phenylethylamine, 1,2-dimethylimidazole, and2-methylimidazole.

The amine-terminated compound may also be blended with additionalpolyols, as discussed below with respect to the polyurethane prepolymersof the invention, to formulate copolymers that are reacted with excessisocyanate to form the polyurea prepolymer. Once a polyol is used,however, the excess isocyanate in the polyurea prepolymer reacts withthe hydroxyl groups in the polyol and forms urethane linkages, whichresults in a composition that is no longer pure polyurea, but instead apolyurea/urethane composition. Such a composition is distinct from apolyurea composition including only isocyanate, an amine-terminatedcompound, and a curing agent.

Furthermore, by using an amine-terminated component based on ahydrophobic segment, the polyurea-based compositions of the inventionmay be more water resistant than those polyurea compositions formed withan amine-terminated hydrophilic segment. Thus, in one embodiment, theamine-terminated compound includes a hydrophobic backbone, e.g., anunsaturated or saturated hydrocarbon-based amine-terminated compound.One example of an amine-terminated hydrocarbon is an amine-terminatedpolybutadiene.

As briefly mentioned above, a polyurethane prepolymer, according to thepresent invention, is the reaction product of a polyol and anisocyanate. Any polyol available to one of ordinary skill in the art issuitable for use in the polyurethane prepolymer. Exemplary polyolsinclude, but are not limited to, polyether polyols, polycaprolactonepolyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols,and mixtures thereof. Both saturated and unsaturated polyols aresuitable for use with the present invention.

Suitable polyether polyols for use in the present invention include, butare not limited to, polytetramethylene ether glycol (PTMEG); copolymerof polytetramethylene ether glycol and 2-methyl-1,4-butane diol (PTG-L);poly(oxyethylene) glycol; poly(oxypropylene) glycol; ethylene oxidecapped (polyoxypropylene) glycol; poly(oxypropylene oxyethylene) glycol;and mixtures thereof.

Suitable polycaprolactone polyols include, but not limited to,diethylene glycol initiated polycaprolactone; propylene glycol initiatedpolycaprolactone; 1,4-butanediol initiated polycaprolactone; trimethylolpropane initiated polycaprolactone; neopentyl glycol initiatedpolycaprolactone; 1,6-hexanediol initiated polycaprolactone;polytetramethylene ether glycol (PTMEG) initiated polycaprolactone;ethylene glycol initiated polycaprolactone; dipropylene glycol initiatedpolycaprolactone; and mixtures thereof.

Suitable polyester polyols include, but not limited to, polyethyleneadipate glycol; polyethylene propylene adipate glycol; polybutyleneadipate glycol; polyethylene butylene adipate glycol; polyhexamethyleneadipate glycol; polyhexamethylene butylene adipate glycol;ortho-phthalate-1,6-hexanediol polyester polyol; polyethyleneterephthalate polyester polyols; and mixtures thereof.

Examples of polycarbonate polyols that may be used with the presentinvention include, but is not limited to, poly(phthalate carbonate)glycol, poly(hexamethylene carbonate) glycol, polycarbonate polyolscontaining bisphenol A, and mixtures thereof.

Hydrocarbon polyols include, but not limited to, hydroxy-terminatedliquid isoprene rubber (LIR), hydroxy-terminated polybutadiene polyol,hydroxy-terminated polyolefin polyols, hydroxy-terminated hydrocarbonpolyols, and mixtures thereof.

Other polyols that may be used to form the prepolymer of the inventioninclude, but not limited to, glycerols; castor oil and its derivatives;Polytail H; Polytail HA; Kraton polyols; acrylic polyols; acidfunctionalized polyols based on a carboxylic, sulfonic, or phosphoricacid group; dimer alcohols converted from the saturated dimerized fattyacid; and mixtures thereof.

By using polyols based on a hydrophobic backbone, the polyurethanecompositions of the invention may be more water resistant than thosepolyurethane compositions having polyols without a hydrophobic backbone.Some non-limiting examples of polyols based on a hydrophobic backboneinclude hydrocarbon polyols, hydroxy-terminated polybutadiene polyols,polyethers, polycaprolactones, and polyesters.

Once formed the polyurea prepolymer or polyurethane prepolymer may bereacted with a functionalized block copolymer. For example, a polyureaprepolymer formed from an isocyanate and a amine-terminated componentmay be reacted with a functionalized olefinic block copolymer having thegeneral structure of AB block copolymer or ABA block copolymer such thatthe functional groups of the block copolymer react with the NCO groupsof the prepolymer.

Reacting a Prepolymer and a Functionalized Block Copolymer and CuringAgent

The compositions of the invention may also be formed using thefunctionalized block copolymers and prepolymer discussed above to forman intermediate prepolymer, which is then cured with a curing agent. Forexample, excess prepolymer is reacted with a block copolymer havingfunctional groups to form an intermediate prepolymer that has the blockinside with the NCO groups on the ends. The polyurea-based compositionor polyurethane-based composition is then formed by chain extending theintermediate prepolymer with a single curing agent or a blend of curingagents. The curing agent may be hydroxy-terminated, amine-terminated, ora combination thereof. Both types of curing agents, i.e.,hydroxy-terminated and amine curatives, may include one or moresaturated, unsaturated, aromatic, and cyclic groups. Additionally, thehydroxy-terminated and amine curatives may include one or more halogengroups.

The type of curing agent used, however, ultimately determines whetherthe composition of the invention is polyurea/urea, polyurea/urethane,polyurethane/urethane or polyurethane/urea. For example, when ahydroxy-terminated curing agent is reacted with a polyurea prepolymer ofthe present invention, the excess isocyanate in the polyurea prepolymerreacts with the hydroxyl groups in the curing agent and forms urethanelinkages, which results in a composition that is no longer purepolyurea, but instead a polyurea/urethane composition. In addition, apolyurethane prepolymer cured with a hydroxy-terminated curing agent ispolyurethane/urethane because any excess isocyanate groups will reactwith the hydroxyl groups of the curing agent to create more urethanelinkages. And, if an amine-terminated curing agent is used with thepolyurethane prepolymer, the excess isocyanate groups will react withthe amine groups of the amine-terminated curing agent to create urealinkages resulting in polyurethane/urea composition.

Thus, for the purposes of the present invention, a pure polyureacomposition, i.e., a polyurea/urea, contains only urea linkages havingthe following general structure:

where x is the chain length, i.e., about 1 or greater, and R and R₁ arestraight chain or branched hydrocarbon chain having about 1 to about 20carbons. On the other hand, a polyurethane/urethane composition containsonly urethane linkages, wherein the urethane linkages have the followinggeneral structure:

where x is the chain length, i.e., about 1 or greater, and R and R₁ arestraight chain or branched hydrocarbon chain having about 1 to about 20carbons. Likewise, a polyurea/urethane composition or polyurethane/ureacomposition contains both urethane and urea linkages.

Thus, the intermediate prepolymers discussed above may be cured with anamine-terminated component. For example, when the compositions of theinvention are polyurea-based, the intermediate prepolymer is formedby 1) forming a polyurea prepolymer from an isocyanate and anamine-terminated component, 2) reacting an excess of the polyureaprepolymer with a functionalized block copolymer to form an intermediateprepolymer having the block inside of two NCO groups, and 3) chainextending the intermediate prepolymer with an amine-terminated curingagent. When forming a polyurea-based composition, the amine-terminatedcuring agent is preferably a secondary diamine curing agent so that thecomposition contains only urea linkages.

Suitable amine-terminated curing agents include, but are not limited to,ethylene diamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; 4,4′-dicyclohexylmethane diamine;1,4-cyclohexane-bis-(methylamine); 1,3-cyclohexane-bis-(methylamine),isomers, and mixtures thereof; diethylene glycol bis-(aminopropyl)ether;2-methylpentamethylene-diamine; diaminocyclohexane, isomers, andmixtures thereof; diethylene triamine; triethylene tetramine;tetraethylene pentamine; propylene diamine; 1,3-diaminopropane;dimethylamino propylamine; diethylamino propylamine;imido-bis-(propylamine); monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; 4,4′-methylenebis-(2-chloroaniline);3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine;3,5-diethylthio-2,6-toluenediamine;4,4′-bis-(sec-butylamino)-diphenylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-benzene; 1,2-bis-(sec-butylamino)-benzene;N,N′-dialkylamino-diphenylmethane;trimethyleneglycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate;4,4′-methylenebis-(3-chloro-2,6-diethyleneaniline);4,4′-methylenebis-(2,6-diethylaniline); meta-phenylenediamine;paraphenylenediamine; N,N′-diisopropyl-isophoronediamine;polyoxypropylene diamine; propylene oxide-based triamine;3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof. Inone embodiment, the amine-terminated curing agent is4,4′-bis-(sec-butylamino)-dicyclohexylmethane. In one embodiment, theamine-terminated curing agent may have a molecular weight of about 64 orgreater. In another embodiment, the molecular weight of the amine-curingagent is about 2000 or less. In addition, any of the amine-terminatedmoieties listed above may be used as curing agents to react with theprepolymers.

Of the list above, the saturated amine-terminated curing agents suitablefor use with the present invention include, but are not limited to,ethylene diamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis-(methylamine);1,3-cyclohexane-bis-(methylamine); diethylene glycolbis-(aminopropyl)ether; 2-methylpentamethylene-diamine;diaminocyclohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; propylene diamine; dipropylene triamine;1,3-diaminopropane; dimethylamino propylamine; diethylamino propylamine;imido-bis-(propylamine); monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;triisopropanolamine; isophoronediamine; N,N′-diisopropylisophoronediamine and mixtures thereof.

In one embodiment, the curatives used with the prepolymer include3,5-dimethylthio-2,4-toluenediamine,3,5-dimethyl-thio-2,6-toluenediamine,4,4′-bis-(sec-butylamino)-diphenylmethane, N,N′-diisopropyl-isophoronediamine; polyoxypropylene diamine; propylene oxide-based triamine;3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof.

As briefly discussed above, many amines may be unsuitable for reactionwith the isocyanate because of the rapid reaction between the twocomponents. In general, unhindered primary diamines are fast reacting.In one embodiment, however, a hindered secondary diamine may be suitablefor use in the prepolymer. Without being bound to any particular theory,it is believed that an amine with a high level of stearic hindrance,e.g., a tertiary butyl group on the nitrogen atom, has a slower reactionrate than an amine with no hindrance or a low level of hindrance. Forexample, 4,4′-bis-(sec-butylamino)-dicyclohexylmethane (Clearlink 1000)may be suitable for use in combination with an isocyanate to form thepolyurea prepolymer. In addition, N,N′-diisopropyl-isophorone diamine,available from Huntsman Corporation under the tradename Jefflink, may beused as the secondary diamine curing agent.

To further improve the shear resistance of the resulting polyureaelastomers, a trifunctional curing agent can be used to help improvecross-linking. Preferably, a triol such as trimethylolpropane or atetraol such as N,N, N′,N′-tetrakis(2-hydroxylpropyl)ethylenediamine maybe added to the formulations.

The intermediate prepolymers of the invention may also be cured with asingle hydroxy-terminated curing agent or a mixture ofhydroxy-terminated curing agents. As mentioned above, if ahydroxy-terminated curing agent is used with a polyurea prepolymer ofthe invention, the resulting composition will include both urea andurethane linkages.

Conversely, if a hydroxy-terminated curing agent is used with apolyurethane prepolymer, the resulting composition will include onlyurethane linkages. For example, when the compositions of the inventionare polyurethane-based, the intermediate prepolymer may formed by 1)forming a polyurethane prepolymer from an isocyanate and a polyol orhydroxy-terminated component, 2) reacting an excess of the polyurethaneprepolymer with a functionalized block copolymer to form an intermediateprepolymer having the block inside of two NCO groups, and 3) chainextending the intermediate prepolymer with a hydroxy-terminated curingagent.

Suitable hydroxy-terminated curing agents include, but are not limitedto, ethylene glycol; diethylene glycol; polyethylene glycol; propyleneglycol; 2-methyl-1,3-propanediol; 2,-methyl-1,4-butanediol; dipropyleneglycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol;1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol;trimethylolpropane; cyclohexyldimethylol; triisopropanolamine;N,N,N′N′-tetra-(2-hydroxypropyl)-ethylene diamine; diethylene glycolbis-(aminopropyl)ether; 1,5-pentanediol; 1,6-hexanediol;1,3-bis-(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexyldimethylol;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]cyclohexane;1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane;polytetramethylene ether glycol, preferably having a molecular weightranging from about 250 to about 3900;resorcinol-di-(beta-hydroxyethyl)ether and its derivatives;hydroquinone-di-(beta-hydroxyethyl)ether and its derivatives;1,3-bis-(2-hydroxyethoxy)benzene;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene;1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}benzene;N,N-bis(β-hydroxypropyl)aniline; 2-propanol-1,1′-phenylaminobis; andmixtures thereof.

The hydroxy-terminated curing agent may have a molecular weight of atleast about 50. In one embodiment, the molecular weight of thehydroxy-terminated curing agent is about 2000 or less. In yet anotherembodiment, the hydroxy-terminated curing agent has a molecular weightof about 250 to about 3900. It should be understood that molecularweight, as used herein, is the absolute weight average molecular weightand would be understood as such by one of ordinary skill in the art.

The saturated hydroxy-terminated curing agents, included in the listabove, are preferred when making a light stable composition. Thosesaturated hydroxy-terminated curing agents include, but are not limitedto, ethylene glycol; diethylene glycol; polyethylene glycol; propyleneglycol; 2-methyl-1,3-propanediol; 2,-methyl-1,4-butanediol; dipropyleneglycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol;1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol;trimethylolpropane; cyclohexyldimethylol; triisopropanolamine;N,N,N′,N′-tetra-(2-hydroxypropyl)-ethylene diamine; diethylene glycolbis-(aminopropyl)ether; 1,5-pentanediol; 1,6-hexanediol;1,3-bis-(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexyldimethylol;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]cyclohexane;1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane;polytetramethylene ether glycol having molecular weight ranging fromabout 250 to about 3900; and mixtures thereof.

In one embodiment, the curing agent is a modified curative blend asdisclosed in co-pending U.S. Patent Publication No. 2003/0212240, whichis incorporated by reference herein in its entirety. For example, thecuring agent of the invention may be modified with a freezing pointdepressing agent to create a curative blend with a slower onset ofsolidification and with storage stable pigment dispersion. A number ofamine-terminated curing agents have relatively high freezing points,e.g., hexamethylene diamine (105.8° F.), diethanolamine (82.4° F.),triethanol amine (69.8° F.), diisopropanolamine (73.4° F.), andtriisopropanolamine (111.2° F.). Such amine-terminated curing agents maybe modified with an amine-terminated freezing point depressing agent ora mixture of amine-terminated freezing point depressing agents. Suitableamine-terminated freezing point depressing agents include, but are notlimited to, ethylene diamine, 1,3-diaminopropane, dimethylaminopropylamine, tetraethylene pentamine, 1,2-propylenediamine,diethylaminopropylamine, 2,2,4-trimethyl-1,6-hexanediamine,2,4,4-trimethyl-1,6-hexanediamine, and mixtures thereof.

The freezing point depressing agent is preferably added in an amountsufficient to reduce the freezing point of the curing agent by asuitable amount to prevent loss of pigment dispersion, but not affectthe physical properties of the golf ball. In one embodiment, thefreezing point depressing agent is added to the curing agent in anamount of about 5 percent or greater by weight of the curative blend,i.e., curing agent(s), freezing point depressing agent. In anotherembodiment, the freezing point depressing agent is present in an amountof about 8 percent greater by weight of the curative blend. In stillanother embodiment, the freezing point depressing agent is present in anamount of about 10 percent or greater. In yet another embodiment, thecurative blend includes the freezing point depressing agent in an amountof about 12 percent or greater by weight of the curative blend. Thecurative blend may also include a freezing point depressing agent in anamount of about 14 percent or greater by weight of the curative blend.

In addition, after freezing and subsequent thawing, the modifiedcurative blend of the present invention preferably has a pigmentdispersion of greater than 0 on the Hegman scale, preferably about 1 orgreater, and more preferably about 2 or greater. In one embodiment, themodified curative blend after a freeze/thaw cycle has a pigmentdispersion of about 3 or greater on the Hegman scale. In anotherembodiment, the modified curative blend after a freeze and thaw is about4 or greater on the Hegman scale, preferably about 5 or greater. Instill another embodiment, the modified curative blend after a freeze andthaw is about 6 or greater on the Hegman scale. In yet anotherembodiment, the modified curative blend after freezing and thawing isabout 7 or greater on the Hegman scale.

Reacting a Prepolymer (or Components Thereof) With a Curing Agent

The compositions of the invention may also be formed by chain extendingthe polyurea prepolymers or polyurethane prepolymers with any suitablecuring agent discussed above. For example, a polyurea-based compositionof the invention may be formed by chain extending a polyurea prepolymerwith an amine-terminated curing agent, preferably a secondary diaminecuring agent. In addition, a polyurethane-based composition of theinvention may be formed by chain extending a polyurethane prepolymerwith a hydroxy-terminated curing agent.

Furthermore, polyurea/urethane or polyurethane/urea compositions may beformed by using a mixture of curing agents. For example, apolyurea/urethane composition may be formed by chain extending apolyurea prepolymer with a single hydroxy-terminated curing agents or ablend including a hydroxy-terminated curing agent.

There are two basic techniques used to process the compositions of theinvention: the one-shot technique and the prepolymer technique. Theone-shot technique reacts the isocyanate, the amine-terminated compoundor polyol depending on whether the desired resultant composition ispolyurea-based or polyurethane-based, and the curing agent in one step,whereas the prepolymer technique requires a first reaction between theamine-terminated compound or polyol and an isocyanate to produce theprepolymer, and a subsequent reaction between the prepolymer and acuring agent. Either method may be employed to produce thepolyurea-based and polyurethane-based compositions of the invention,however, the prepolymer technique is preferred because it providesbetter control of chemical reaction and, consequently, results in moreuniform properties for the elastomers.

Depending on the prepolymer to curative ratio, which is a function ofthe NCO content of the prepolymer and molecular weight of the curingagent, the castable polyurea-based or polyurethane-based compositions ofthe invention may be thermoset or thermoplastic in nature. For example,castable thermoplastic compositions of the invention include linearpolymers and are typically formed curing the prepolymer with a diol orsecondary diamine with 1:1 stoichiometry in the absence of moisture.Thermoset compositions of the invention, on the other hand, arecross-linked polymers and are typically produced from the reaction of adiisocyanate and a polyol cured with a primary diamine or polyfunctionalglycol. In an alternative embodiment, thermoset polyurethanes may beformed when using a secondary diamine when the prepolymer to curativeratio is less than about 1. For example, the composition may bethermoset polyurethane when the prepolymer to secondary diamine curingagent is 1:0.95.

In addition, skilled artisans are aware that the various properties ofthe golf ball and golf ball components, e.g., hardness, may becontrolled by adjusting the prepolymer-curative ratio. For example, theratio of a polyurea prepolymer with 6 percent unreacted NCO groups curedwith 1,4-butanediol is 15.6:1, whereas the ratio of the same prepolymercured with 4,4′-bis-(sec-butylamino)-dicyclohexylmethane (Clearlink1000) is 4.36:1. The ratio of prepolymer to curing agent for thepurposes of this invention is preferably from about 0.5:1 to about 16:1.

Because the prepolymer-curative ratio determines whether a compositionof the invention will be thermoplastic or thermoset, the method ofmolding the compositions of the invention onto the ball also will varydepending on the composition. For example, thermoplastic polyureacompositions of the present invention may be used to make thermoplasticpellets that can be molded onto the ball by injection molding orcompression molding. Thermoset polyurea compositions may be cast ontothe ball. In addition, both the thermoplastic and thermoset polyureacompositions of the present invention also may be formed around the coreusing reaction injection molding (RIM) and liquid injection molding(LIM) techniques.

Composition Additives

Additional materials conventionally included in polyurethane andpolyurea compositions may be added to the polyurethane and polyureaprepolymers, the modified curative blends, or the composite compositionsof the invention. These additional materials include, but are notlimited to, catalysts, wetting agents, coloring agents, opticalbrighteners, crosslinking agents, whitening agents such as TiO₂ and ZnO,UV absorbers, hindered amine light stabilizers, defoaming agents,processing aids, surfactants, and other conventional additives. Forexample, wetting additives may be added to the modified curative blendsof the invention to more effectively disperse the pigment(s). Suitablewetting agents are available from Byk-Chemle and Crompton Corporation,among others.

Antioxidants, stabilizers, softening agents, plasticizers, includinginternal and external plasticizers, impact modifiers, foaming agents,density-adjusting fillers, reinforcing materials, and compatibilizersmay also be added to any composition of the invention. Those of ordinaryskill in the art are aware of the purpose of these additives and theamounts that should be employed to fulfill those purposes.

Catalysts

A catalyst may also be employed to promote the reaction between theprepolymer and the curing agent for both the polyurethane and polyureacompositions. Suitable catalysts include, but are not limited to bismuthcatalyst; zinc octoate; stannous octoate; tin catalysts such asbis-butyltin dilaurate (DABCO® T-12 manufactured by Air Products andChemicals, Inc.), bis-butyltin diacetate (DABCO® T-1); stannous octoate(DABCO® T-9); tin (II) chloride, tin (IV) chloride, bis-butyltindimethoxide (FASCAT®-4211), dimethyl-bis[1-oxonedecyl)oxy]stannane(FORMEZ® UL-28), di-n-octyltin bis-isooctyl mercaptoacetate (FORMEZ®UL-29); amine catalysts such as triethylenediamine (DABCO® 33-LV),triethylamine, and tributylamine; organic acids such as oleic acid andacetic acid; delayed catalysts such as POLYCAT™ SA-1, POLYCAT™ SA-2,POLYCAT™, and the like; and mixtures thereof. In one embodiment, thecatalyst is bis-butyltin dilaurate. The catalyst is preferably added inan amount sufficient to catalyze the reaction of the components in thereactive mixture. In one embodiment, the catalyst is present in anamount from about 0.001 percent to about 5 percent by weight of thecomposition. For example, when using a tin catalyst, such asbis-butyltin dilaurate, the catalyst is preferably present in an amountfrom about 0.005 percent to about 1 percent. In another embodiment, thecatalyst is present in an amount of about 0.05 weight percent orgreater. In another embodiment, the catalyst is present in an amount ofabout 0.5 weight percent or greater.

Use of low levels of tin catalysts, typically from about 0 to about 0.04weight percent of the total composition, requires high temperatures toachieve a suitable reaction rate, which may result in degradation of theprepolymer. Increasing the amount of catalysts to unconventional highlevels enables the reduction in process temperatures while retainingcomparable cure stages. Use of the higher catalyst level also allows themixing speeds to be reduced. Thus, in one embodiment, the tin catalystis present in an amount from about 0.01 percent to about 0.55 percent byweight of the composition. In another embodiment, about 0.05 percent toabout 0.4 percent of tin catalyst is present in the composition. In yetanother embodiment, the tin catalyst is present in an amount from about0.1 percent to about 0.25 percent.

Density-Adjusting Filler(s)

Fillers may be added to the polyurethane and polyurea compositions ofthe invention to affect rheological and mixing properties, the specificgravity (i.e., density-modifying fillers), the modulus, the tearstrength, reinforcement, and the like. The fillers are generallyinorganic, and suitable fillers include numerous metals, metal oxidesand salts, such as zinc oxide and tin oxide, as well as barium sulfate,zinc sulfate, calcium carbonate, zinc carbonate, barium carbonate, clay,tungsten, tungsten carbide, an array of silicas, regrind (recycled corematerial typically ground to about 30 mesh particle),high-Mooney-viscosity rubber regrind, and mixtures thereof.

For example, the compositions of the invention can be reinforced byblending with a wide range of density-adjusting fillers, e.g., ceramics,glass spheres (solid or hollow, and filled or unfilled), and fibers,inorganic particles, and metal particles, such as metal flakes, metallicpowders, oxides, and derivatives thereof, as is known to those withskill in the art. The selection of such filler(s) is dependent upon thetype of golf ball desired, i.e., one-piece, two-piece, multi-component,or wound, as will be more fully detailed below. Generally, the fillerwill be inorganic, having a density of greater than 4 g/cc, and will bepresent in amounts between about 5 and about 65 weight percent based onthe total weight of the polymer components included in the layer(s) inquestion. Examples of useful fillers include zinc oxide, barium sulfate,calcium oxide, calcium carbonate, and silica, as well as other knowncorresponding salts and oxides thereof.

Fillers may also be used to modify the weight of the core or at leastone additional layer for specialty balls, e.g., a lower weight ball ispreferred for a player having a low swing speed.

Blowing or Foaming Agent(s)

The compositions of the invention may be foamed by the addition of theat least one physical or chemical blowing or foaming agent. The use of afoamed polymer allows the golf ball designer to adjust the density ormass distribution of the ball to adjust the angular moment of inertia,and, thus, the spin rate and performance of the ball. Foamed materialsalso offer a potential cost savings due to the reduced use of polymericmaterial.

Blowing or foaming agents useful include, but are not limited to,organic blowing agents, such as azobisformamide; azobisisobutyronitrile;diazoaminobenzene; N,N-dimethyl-N,N-dinitrosoterephthalamide;N,N-dinitrosopentamethylene-tetramine; benzenesulfonyl-hydrazide;benzene-1,3-disulfonyl hydrazide; diphenylsulfon-3-3, disulfonylhydrazide; 4,4′-oxybisbenzene sulfonyl hydrazide; p-toluene sulfonylsemicarbizide; barium azodicarboxylate; butylamine nitrile; nitroureas;trihydrazino triazine; phenyl-methyl-uranthan; p-sulfonhydrazide;peroxides; and inorganic blowing agents such as ammonium bicarbonate andsodium bicarbonate. A gas, such as air, nitrogen, carbon dioxide, etc.,can also be injected into the composition during the injection moldingprocess.

Additionally, a foamed composition of the present invention may beformed by blending microspheres with the composition either during orbefore the molding process. Polymeric, ceramic, metal, and glassmicrospheres are useful in the invention, and may be solid or hollow andfilled or unfilled. In particular, microspheres up to about 1000micrometers in diameter are useful. Furthermore, the use of liquidnitrogen for foaming, as disclosed in U.S. Pat. No. 6,386,992, which isincorporated by reference herein, may produce highly uniform foamedcompositions for use in the present invention.

Either injection molding or compression molding may be used to form alayer including a foamed polymeric material. For example, a compositionof the present invention can be thermoformed and, thus, can becompression molded. For compression molded grafted metallocene catalyzedpolymer blend layers, half-shells may be made by injection molding agrafted metallocene catalyzed polymer blend in a conventional half-shellmold or by compression molding sheets of foamed grafted metallocenecatalyzed polymer. The half-shells are placed about a previously formedcenter or core, cover, or mantle layer, and the assembly is introducedinto a compression molding machine, and compression molded at about 250°F. to 400° F. The molded balls are then cooled while still in the mold,and finally removed when the layer of grafted metallocene catalyzedpolymer blend is hard enough to be handled without deforming. Additionalcore, mantle, and cover layers are then molded onto the previouslymolded layers, as needed, until a complete ball is formed.

Light Stabilizers

The compositions of the invention may include both saturated andunsaturated components. And, while the use of only saturated componentsaids in avoiding the yellowing over time that occurs with unsaturatedcomponents, the use of various UV absorbers and light stabilizers to anyof the above compositions may help to also maintain the tensilestrength, elongation, and color stability. The use of light stabilizingcomponents also may assist in preventing cover surface fractures due tophotodegredation.

As such, the compositions of the invention may contain at least onelight stabilizing component to prevent significant yellowing fromunsaturated components contained therein. The use of a light stabilizeris preferred, for instance, for compositions having a difference inyellowness (ΔY) of about 15 or greater, but also may be added tocompositions having a difference in yellowness of from about 12 to about15. As used herein, light stabilizer may be understood to includehindered amine light stabilizers, ultraviolet (UV) absorbers, andantioxidants.

Suitable light stabilizers include, but are not limited to, TINUVIN®292, TINUVIN® 328, TINUVIN® 213, TINUVIN® 765, TINUVIN® 770 and TINUVIN®622. TINUVIN® products are available from Ciba Specialty Chemicals ofTarrytown, N.Y. In one embodiment, the light stabilizer is UV absorberTINUVIN® 328, which is useful with aromatic compounds. In anotherembodiment, hindered amine light stabilizer TINUVIN® 765 is used witharomatic or aliphatic compounds. In addition, TINUVIN® 292 may also beused with the aromatic or aliphatic compositions of the invention.

As discussed above, dyes, as well as optical brighteners and fluorescentpigments may also be included in the golf ball covers produced withpolymers formed according to the present invention. Such additionalingredients may be added in any amounts that will achieve their desiredpurpose.

To further improve the shear resistance and heat resistance of theresulting polyurea elastomers, a multi-functional curing agent can beused to help improve cross-linking. In one embodiment of the presentinvention, the multi-functional curing agent is modified with acompatible freezing point depressing agent as detailed above. Forexample, a triol such as trimethylolpropane or a tetraol such as N,N,N′,N′-tetrakis(2-hydroxylpropyl) ethylenediamine may be added to thecomposition. In one embodiment, a primary diamine, such as3,3′-dimethyl-4,4′-diaminodicyclohexylmethane or4,4′-diaminodicyclohexylmethane is added to the polyurea composition.Useful triamine curing agents for improving the crosslinking of polyureaelastomers include, but are not limited to: propylene oxide-basedtriamines; trimethylolpropane-based triamines; glycerin-based triamines;N,N-bis {2-[(aminocarbonyl)amino]ethyl}-urea;N,N′,N″-tris(2-aminoethyl)-methanetriamine;N1-(5-aminopentyl)-1,2,6-hexanetriamine; 1,1,2-ethanetriamine;N,N′,N″-tris(3-aminopropyl)-methanetriamine;N1-(2-aminoethyl)-1,2,6-hexanetriamine;N1-(10-aminodecyl)-1,2,6-hexanetriamine; 1,9,18-octadecanetriamine;4,10,16,22-tetraazapentacosane-1,13,25-triamine;N1-{3-[[4-[(3-aminopropyl)amino]butyl]amino]propyl}-1,2,6-hexanetriamine;di-9-octadecenyl-(Z,Z)-1,2,3-propanetriamine; 1,4,8-octanetriamine;1,5,9-nonanetriamine; 1,9,10-octadecanetriamine; 1,4,7-heptanetriamine;1,5,10-decanetriamine; 1,8,17-heptadecanetriamine; 1,2,4-butanetriamine;propanetriamine; 1,3,5-pentanetriamine;N1-{3-[[4-[(3-aminopropyl)amino]butyl]amino]propyl}-1,2,6-hexanetriamine;N1-{4-[(3-aminopropyl)amino]butyl}-1,2,6-hexanetriamine;2,5-dimethyl-1,4,7-heptanetriamine;N1-(6-aminohexyl)-1,2,6-hexanetriamine;6-ethyl-3,9-dimethyl-3,6,9-undecanetriamine; 1,5,11-undecanetriamine;1,6,11-undecanetriamine; N,N-bis(aminomethyl)-methanediamine;N,N-bis(2-aminoethyl)-1,3-propanediamine; methanetriamine;N1-(2-aminoethyl)-N2-(3-aminopropyl)-1,2,5-pentanetriamine;N1-(2-aminoethyl)-1,2,6-hexanetriamine;2,6,11-trimethyl-2,6,11-dodecanetriamine; 1,1,3-propanetriamine;6-(aminomethyl)-1,4,9-nonanetriamine; 1,2,6-hexanetriamine;N2-(2-aminoethyl)-1,1,2-ethanetriamine; 1,3,6-hexanetriamine;N,N-bis(2-aminoethyl)-1,2-ethanediamine;3-(aminomethyl)-1,2,4-butanetriamine; 1,1,1-ethanetriamine;N1,N1-bis(2-aminoethyl) 1,2-propanediamine; 1,2,3-propanetriamine;2-methyl-1,2,3-propanetriamine; and mixtures thereof.

Fragrance Components

Some materials used in the polyurea or polyurethane compositions of theinvention are odorous in nature or produce odors during reaction withother materials or with oxygen. For example, the odor of curativeEthacure 300 is attributed to dimethyl disulfide (DMDS) once the productreacts with oxygen. As used herein, a material or component is odorouswhen the odor threshold surpasses a threshold of 0.029 mg/m³ in air. Afragrance or masking component may be added to the compositions of theinvention to eliminate odors. The fragrance component is preferablyadded in an amount of about 0.01 percent to about 1.5 percent by weightof the composition. In one embodiment, the fragrance component is addedto the composition in an amount of about 0.03 percent or greater byweight of the composition. In another embodiment, the fragrancecomponent is added to the composition in an amount of about 1.2 percentor less by weight of the composition. In yet another embodiment, thefragrance component is added in an amount of about 0.5 percent to about1 percent by weight of the composition. For example, an optimum loadingof the fragrance component may be about 0.08 percent by weight of thecomposition, but adding more may enhance the effect if needed.

Suitable fragrance components include, but are not limited to, LongLasting Fragrance Mask #59672, Long Lasting Fragrance Mask #46064, LongLasting Fragrance Mask #55248, Non-Descript Fragrance Mask #97779, Freshand Clean Fragrance Mask #88177, and Garden Fresh Fragrance Mask #87473,all of which are manufactured by Flavor and Fragrance Specialties ofMahwah, N.J. Other non-limiting examples of fragrance components thatmay be added to the compositions of the invention include benzaldehyde,benzyl benzoate, benzyl propionate, benzyl salicylate, benzyl alcohol,cinnamic aldehydes, natural and essential oils derived from botanicalsources, and mixtures thereof.

Composition Blends

The compositions of the invention preferably include from about 1percent to about 100 percent polyurea-based polymers orpolyurethane-based polymers, however, the compositions may also beblended with other materials. In one embodiment, the compositioncontains about 10 percent to about 90 percent polyurea-based polymer orpolyurethane-based polymer, preferably from about 10 percent to about 75percent polyurea-based polymer or polyurethane-based polymer, andcontains about 90 percent to 10 percent, more preferably from about 90percent to about 25 percent other polymers and/or other materials asdescribed below. Unless otherwise stated herein, all percentages aregiven in percent by weight of the total composition of the golf balllayer in question.

Other polymeric materials suitable for blending with the compositions ofthe invention include castable thermoplastics, cationic and anionicurethane ionomers and urethane epoxies, polyurethane ionomers, polyureaionomers, epoxy resins, polyethylenes, polyamides and polyesters,polycarbonates, polyacrylin, siloxanes and epoxy resins or their blends,and mixtures thereof. One of ordinary skill in the art would be wellaware of methods to blend the polymeric materials with the compositionof the invention.

Examples of suitable urethane ionomers are disclosed in U.S. Pat. No.5,692,974, the disclosure of which is hereby incorporated by referencein its entirety. Other examples of suitable polyurethanes are describedin U.S. Pat. No. 5,334,673, the entire disclosure of which isincorporated by reference herein. Examples of suitable polyureas used toform the polyurea ionomer listed above are discussed in U.S. Pat. No.5,484,870. In particular, the polyureas of U.S. Pat. No. 5,484,870 areprepared by reacting a polyisocyanate and a polyamine curing agent toyield polyurea, which are distinct from the polyureas of the presentinvention which are formed from a polyurea prepolymer and curing agent.Examples of suitable polyurethanes cured with epoxy group containingcuring agents are disclosed in U.S. Pat. No. 5,908,358. The disclosuresof the above patents are incorporated herein by reference in theirentirety.

The polyurea-based compositions and polyurethane-based compositions ofthe invention may also be in the form of a blend with at least onehighly neutralized polymer. For example, a prepolymer can be chainextended with a curing agent and then blended with a highly neutralizedpolymer. Suitable highly neutralized polymers include, but are notlimited to, polymers containing α,β-unsaturated carboxylic acid groups,or the salts thereof, that have been highly neutralized by organic fattyacids. The organic acids are aliphatic, mono-functional (saturated,unsaturated, or multi-unsaturated) organic acids. Salts of these organicacids may also be employed. The salts of organic acids of the presentinvention include the salts of barium, lithium, sodium, zinc, bismuth,chromium, cobalt, copper, potassium, strontium, titanium, tungsten,magnesium, cesium, iron, nickel, silver, aluminum, tin, or calcium,salts of fatty acids, particularly stearic, behenic, erucic, oleic,linoleic, or dimerized derivatives thereof. It is preferred that theorganic acids and salts of the present invention be relativelynon-migratory (they do not bloom to the surface of the polymer underambient temperatures) and non-volatile (they do not volatilize attemperatures required for melt-blending). The acid moieties of thehighly-neutralized polymers (“HNP”), typically ethylene-based ionomers,are preferably neutralized greater than about 70 percent, morepreferably greater than about 90 percent, and most preferably at leastabout 100 percent.

Acid Functionalization of Compositions

The present invention also contemplates the acid functionalization ofthe polyurethane and polyurea compositions of the invention as disclosedin U.S. Pat. No. 6,610,812, which is incorporated by reference herein inits entirety. The acid functional group is preferably based on asulfonic group (HSO₃), carboxylic group (HCO₂), phosphoric acid group(H₂PO₃), or a combination thereof. More than one type of acid functionalgroup may be incorporated into the polyurea or polyurethane.

Golf Ball Core Layer(s)

The cores of the golf balls formed according to the invention may besolid, semi-solid, hollow, fluid-filled or powder-filled, one-piece ormulti-component cores. The term “semi-solid” as used herein refers to apaste, a gel, or the like. Any core material known to one of ordinaryskill in that art is suitable for use in the golf balls of theinvention. Suitable core materials include thermoset materials, such asrubber, styrene butadiene, polybutadiene, isoprene, polyisoprene,trans-isoprene, as well as thermoplastics such as ionomer resins,polyamides or polyesters, and thermoplastic and thermoset polyurethaneelastomers. As mentioned above, the polyurethane or polyureacompositions of the present invention may also be incorporated into anycomponent of a golf ball, including the core. For example, a core layermay contain at least one of the polyurea/urea compositions,polyurea/urethane compositions, polyurethane/urethane compositions, orpolyurethane/urea compositions of the invention.

In one embodiment, the golf ball core is formed from a compositionincluding a base rubber (natural, synthetic, or a combination thereof),a crosslinking agent, and a filler. In another embodiment, the golf ballcore is formed from a reaction product that includes a cis-to-transcatalyst, a resilient polymer component having polybutadiene, a freeradical source, and optionally, a crosslinking agent, a filler, or both.Various combinations of polymers, cis-to-trans catalysts, fillers,crosslinkers, and a source of free radicals, such as those disclosed inco-pending U.S. Patent Publication No. 2003/0119989, the entiredisclosure of which is incorporated by reference herein, may be used toform the reaction product. Although this polybutadiene reaction productis discussed in a section pertaining to core compositions, the presentinvention also contemplates the use of the reaction product to form atleast a portion of any component of a golf ball.

As used herein, the terms core and center are generally usedinterchangeably to reference the innermost component of the ball. Insome embodiments, however, the term “center” is used when there aremultiple core layers, i.e., a center and an outer core layer.

Golf Ball Intermediate Layer(s)

When the golf ball of the present invention includes an intermediatelayer, such as an inner cover layer or outer core layer, i.e., anylayer(s) disposed between the inner core and the outer cover of a golfball, this layer can include any materials known to those of ordinaryskill in the art including thermoplastic and thermosetting materials. Inone embodiment, the intermediate layer is formed, at least in part, fromany of the polyurethane-based and polyurea-based compositions discussedabove.

The intermediate layer(s) may also likewise include one or morehomopolymeric or copolymeric materials, such as:

-   -   (1) Vinyl resins, such as those formed by the polymerization of        vinyl chloride, or by the copolymerization of vinyl chloride        with vinyl acetate, acrylic esters or vinylidene chloride;    -   (2) Polyolefins, such as polyethylene, polypropylene,        polybutylene and copolymers such as ethylene methylacrylate,        ethylene ethylacrylate, ethylene vinyl acetate, ethylene        methacrylic or ethylene acrylic acid or propylene acrylic acid        and copolymers and homopolymers produced using a single-site        catalyst or a metallocene catalyst;    -   (3) Polyurethanes, such as those prepared from polyols and        diisocyanates or polyisocyanates and those disclosed in U.S.        Pat. No. 5,334,673;    -   (4) Polyureas, such as those disclosed in U.S. Pat. No.        5,484,870;    -   (5) Polyamides, such as poly(hexamethylene adipamide) and others        prepared from diamines and dibasic acids, as well as those from        amino acids such as poly(caprolactam), and blends of polyamides        with SURLYN, polyethylene, ethylene copolymers,        ethyl-propylene-non-conjugated diene terpolymer, and the like;    -   (6) Acrylic resins and blends of these resins with poly vinyl        chloride, elastomers, and the like;    -   (7) Thermoplastics, such as urethanes; olefinic thermoplastic        rubbers, such as blends of polyolefins with        ethylene-propylene-non-conjugated diene terpolymer; block        copolymers of styrene and butadiene, isoprene or        ethylene-butylene rubber; or copoly(ether-amide), such as PEBAX,        sold by Atofina Chemicals, Inc. of Philadelphia, Pa.;    -   (8) Polyphenylene oxide resins or blends of polyphenylene oxide        with high impact polystyrene as sold under the trademark NORYL        by General Electric Company of Pittsfield, Mass.;    -   (9) Thermoplastic polyesters, such as polyethylene        terephthalate, polybutylene terephthalate, polyethylene        terephthalate/glycol modified and elastomers sold under the        trademarks HYTREL by E.I. DuPont de Nemours & Co. of Wilmington,        Del., and LOMOD by General Electric Company of Pittsfield,        Mass.;    -   (10) Blends and alloys, including polycarbonate with        acrylonitrile butadiene styrene, polybutylene terephthalate,        polyethylene terephthalate, styrene maleic anhydride,        polyethylene, elastomers, and the like, and polyvinyl chloride        with acrylonitrile butadiene styrene or ethylene vinyl acetate        or other elastomers; and    -   (11) Blends of thermoplastic rubbers with polyethylene,        propylene, polyacetal, nylon, polyesters, cellulose esters, and        the like.

In one embodiment, the intermediate layer includes polymers, such asethylene, propylene, butene-1 or hexene-1 based homopolymers orcopolymers including functional monomers, such as acrylic andmethacrylic acid and fully or partially neutralized ionomer resins andtheir blends, methyl acrylate, methyl methacrylate homopolymers andcopolymers, imidized, amino group containing polymers, polycarbonate,reinforced polyamides, polyphenylene oxide, high impact polystyrene,polyether ketone, polysulfone, poly(phenylene sulfide),acrylonitrile-butadiene, acrylic-styrene-acrylonitrile, poly(ethyleneterephthalate), poly(butylene terephthalate), poly(ethylene vinylalcohol), poly(tetrafluoroethylene) and their copolymers includingfunctional comonomers, and blends thereof. For example, the intermediatelayer may be formed of low acid ionomers, such as those described inU.S. Pat. Nos. 6,506,130 and 6,503,156, high acid ionomers, highlyneutralized polymers, such as those disclosed in U.S. Patent PublicationNos. 2001/0018375 and 2001/0019971, or mixtures thereof. Theintermediate layer may also be formed from the compositions as disclosedin U.S. Pat. No. 5,688,191. The entire disclosures of these patents andpublications are incorporated herein by express reference thereto.

In another embodiment, the intermediate layer includes at least oneprimarily or fully non-ionomeric thermoplastic material. Suitablenon-ionomeric materials include polyamides and polyamide blends, graftedand non-grafted metallocene catalyzed polyolefins or polyamides,polyamide/ionomer blends, polyamide/nonionomer blends, polyphenyleneether/ionomer blends, and mixtures thereof. Examples of grafted andnon-grafted metallocene catalyzed polyolefins or polyamides,polyamide/ionomer blends, polyamide/nonionomer blends are disclosed inco-pending U.S. Patent Publication No. 2003/0078348, the entiredisclosure of which is incorporated by reference herein. Another exampleof a polyamide-nonionomer blend is a polyamide and non-ionic polymersproduced using non-metallocene single-site catalysts. Examples ofsuitable single-site catalyzed polymers are disclosed in co-pending U.S.Pat. No. 6,476,130, of which the entire disclosure is incorporated byreference herein.

Golf Ball Cover(s)

The cover provides the interface between the ball and a club. Propertiesthat are desirable for the cover are good moldability, high abrasionresistance, high impact resistance, high tear strength, high resilience,and good mold release, among others.

The cover layer may be formed, at least in part, from at least one ofthe polyurethane-based or polyurea-based compositions of the invention.For example, a cover layer may be formed of a polyurea-based compositionthat includes styrene-butadiene-styrene block copolymer.

The cover layer(s) may also be formed from composition blends asdiscussed above. For example, in one embodiment, at least one coverlayer is formed from a blend of about 10 percent to about 90 percent ofa polyurea-based material, preferably saturated, and about 90 percent toabout 10 percent other polymers and/or other materials. In anotherembodiment, at least one cover layer is formed from a blend of about 10percent to about 90 percent of a polyurethane-based material, preferablysaturated, and about 90 percent to about 10 percent other polymersand/or other materials. In yet another embodiment, the covercompositions include from about 10 percent to about 75 percent of apolyurea-based or polyurethane-based material and about 90 percent toabout 25 percent other polymers and/or other materials, such as thoselisted below.

When the polyurethane-based and polyurea-based compositions of theinvention are incorporated into a core or intermediate/inner coverlayer, the cover compositions may include one or more homopolymeric orcopolymeric materials as discussed in the section above pertaining tothe intermediate layer. The cover may also be at least partially formedfrom the polybutadiene reaction product discussed above with respect tothe core.

As discussed elsewhere herein, the composition may be molded onto thegolf ball in any known manner, such as by casting, compression molding,injection molding, reaction injection molding, or the like. One skilledin the art would appreciate that the molding method used may bedetermined at least partially by the properties of the composition. Forexample, casting may be preferred when the material is thermoset,whereas compression molding or injection molding may be preferred forthermoplastic compositions.

Golf Ball Construction

The compositions of the present invention may be used with any type ofball construction including, but not limited to, one-piece, two-piece,three-piece, and four-piece designs, a double core, a double cover, anintermediate layer(s), a multilayer core, and/or a multi-layer coverdepending on the type of performance desired of the ball. That is, thecompositions of the invention may be used in a core, intermediate layer,and/or cover of a golf ball, each of which may have a single layer ormultiple layers. As used herein, the term “multilayer” means at leasttwo layers.

As described above in the core section, a core may be a one-piece coreor a multilayer core, both of which may be solid, semi-solid, hollow,fluid-filled, or powder-filled. A multilayer core is one that has aninnermost component with an additional core layer or additional corelayers disposed thereon. For example, FIG. 1 shows a golf ball 1 havinga core 2 and a cover 3. In one embodiment, the golf ball of FIG. 1represents a core 2 of polybutadiene reaction material or otherconventional materials and a cover 3 including the polyurea-basedcomposition of the invention. In another embodiment, the golf ball ofFIG. 1 represents a core 2 formed from polybutadiene reaction materialand a cover 3 including the polyurethane-based composition of theinvention.

In addition, when the golf ball of the present invention includes anintermediate layer, this layer may be incorporated with a single ormultilayer cover, a single or multi-piece core, with both a single layercover and core, or with both a multilayer cover and a multilayer core.The intermediate layer may be an inner cover layer or outer core layer,or any other layer(s) disposed between the inner core and the outercover of a golf ball. As with the core, the intermediate layer may alsoinclude a plurality of layers. It will be appreciated that any number ortype of intermediate layers may be used, as desired.

FIG. 2 illustrates a multilayer golf ball 11, including a cover 13, atleast one intermediate layer 14, and a core 12. In one embodiment, thegolf ball 11 of FIG. 2 may include a core 12 of polybutadiene reactionmaterial, an intermediate layer 14, and a cover 13 formed of thepolyurea-based composition of the invention. In addition, the golf ball21 of FIG. 3 has a core 22 of polybutadiene reaction material or otherconventional core materials, at least one intermediate layer 24, andcover 23 including at least one polyurethane-based material of thepresent invention. In one embodiment, the intermediate layer 14 isformed of an ionomeric material.

The intermediate layer may also be a tensioned elastomeric materialwound around a solid, semi-solid, hollow, fluid-filled, or powder-filledcenter. As used herein, the term “fluid” refers to a liquid or gas andthe term “semi-solid” refers to a paste, gel, or the like. A wound layermay be described as a core layer or an intermediate layer for thepurposes of the invention. As an example, the golf ball 31 of FIG. 4 mayinclude a core layer 32, a tensioned elastomeric layer 34 wound thereon,and a cover layer 33. In particular, the golf ball 31 of FIG. 4 may havea core 32 made of a polybutadiene reaction product, an intermediatelayer including a tensioned elastomeric material 34 and cover 33including at least one polyurea-based or polyurethane-based compositionof the invention. The tensioned elastomeric material may be formed ofany suitable material known to those of ordinary skill in the art.

In yet another embodiment, the golf ball 41 of FIG. 5 has a hollowspherical core shell 42 with its hollow interior filled with a liquid43, a thread rubber layer including a tensioned elastomeric material 44and a cover 45 including at least one polyurea-based orpolyurethane-based composition of the invention.

Likewise, the cover may include a plurality of layers, e.g., an innercover layer disposed about a golf ball center and an outer cover layerformed thereon. For example, FIG. 6 may represent a golf ball 51 havinga core 52, a thin inner cover layer 54, and a thin outer cover layer 53disposed thereon. In particular, the core 51 may be formed of apolybutadiene reaction material, the inner cover layer 54 formed of anionomer blend, and the outer cover layer 53 formed of the polyurea-basedor polyurethane-based compositions of the invention. In addition, FIG. 7may represent a golf ball 61 having a core 62, an outer core layer 65, athin inner cover layer 64, and a thin outer cover layer 63 disposedthereon. In one embodiment, the core 62 and the outer core layer 65 areformed of the polybutadiene reaction material but differ in hardness,the inner cover layer 64 is formed of an ionomer blend, and the outercover layer 63 is formed of a polyurea-based or polyurethane-basedcomposition of the invention.

Furthermore, the compositions of the invention may be used to form agolf ball 71, shown in FIG. 8, having a large core 72 and a thin outercover layer 73. In one embodiment, the large core 72 is formed of apolybutadiene reaction material and the thin outer cover layer 73 isformed of a polyurea-based or polyurethane-based composition of theinvention.

While hardness gradients are typically used in a golf ball to achievecertain characteristics, the present invention also contemplates thecompositions of the invention being used in a golf ball with multiplecover layers having essentially the same hardness, wherein at least oneof the layers has been modified in some way to alter a property thataffects the performance of the ball. Such ball constructions aredisclosed in co-pending U.S. Patent Publication No. 2003/0232666, theentire disclosure of which is incorporated by reference herein.

Other non-limiting examples of suitable types of ball constructions thatmay be used with the present invention include those described in U.S.Pat. Nos. 6,056,842, 5,688,191, 5,713,801, 5,803,831, 5,885,172,5,919,100, 5,965,669, 5,981,654, 5,981,658, and 6,149,535, as well as inPublication Nos. US2001/0009310 A1, US2002/0025862, and US2002/0028885.The entire disclosures of these patents and published patentapplications are incorporated by reference herein.

Methods of Forming Layers

The golf balls of the invention may be formed using a variety ofapplication techniques such as compression molding, flip molding,injection molding, retractable pin injection molding, reaction injectionmolding (RIM), liquid injection molding (LIM), casting, vacuum forming,powder coating, flow coating, spin coating, dipping, spraying, and thelike. Conventionally, compression molding and injection molding areapplied to thermoplastic materials, whereas RIM, liquid injectionmolding, and casting are employed on thermoset materials. These andother manufacture methods are disclosed in U.S. Pat. Nos. 6,207,784 and5,484,870, the disclosures of which are incorporated herein by referencein their entirety.

The cores of the invention may be formed by any suitable method known tothose of ordinary skill in art. When the cores are formed from athermoset material, compression molding is a particularly suitablemethod of forming the core. In a thermoplastic core embodiment, on theother hand, the cores may be injection molded. Furthermore, U.S. Pat.Nos. 6,180,040 and 6,180,722 disclose methods of preparing dual coregolf balls. The disclosures of these patents are hereby incorporated byreference in their entirety.

The intermediate layer may also be formed from using any suitable methodknown to those of ordinary skill in the art. For example, anintermediate layer may be formed by blow molding and covered with adimpled cover layer formed by injection molding, compression molding,casting, vacuum forming, powder coating, and the like.

The polyurea-based and polyurethane-based materials of the invention maybe applied over the inner ball using a variety of application techniquessuch as spraying, compression molding, dipping, spin coating, casting,or flow coating methods that are well known in the art. In oneembodiment, the polyurea-based or polyurethane-based materials areformed over the core using a combination of casting and compressionmolding. Conventionally, compression molding and injection molding areapplied to thermoplastic cover materials, whereas RIM, liquid injectionmolding, and casting are employed on thermoset cover materials.

U.S. Pat. No. 5,733,428, the entire disclosure of which is herebyincorporated by reference, discloses a method for forming apolyurethane-based cover on a golf ball core. Because this methodrelates to the use of both casting thermosetting and thermoplasticmaterial as the golf ball cover, wherein the cover is formed around thecore by mixing and introducing the material in mold halves, thepolyurea-based compositions may also be used employing the same castingprocess.

For example, once the polyurea-based composition or polyurethane-basedcomposition is mixed, an exothermic reaction commences and continuesuntil the material is solidified around the core. It is important thatthe viscosity be measured over time, so that the subsequent steps offilling each mold half, introducing the core into one half and closingthe mold can be properly timed for accomplishing centering of the corecover halves fusion and achieving overall uniformity. A suitableviscosity range of the curing urea mix for introducing cores into themold halves is determined to be approximately between about 2,000 cP andabout 30,000 cP, with the preferred range of about 8,000 cP to about15,000 cP.

To start the cover formation, mixing of the prepolymer and curative isaccomplished in a motorized mixer inside a mixing head by meteringamounts of the curative and prepolymer through the feed lines. Toppreheated mold halves are filled and placed in fixture units usingcentering pins moving into apertures in each mold. At a later time, thecavity of a bottom mold half, or the cavities of a series of bottom moldhalves, is filled with similar mixture amounts as used for the top moldhalves. After the reacting materials have resided in top mold halves forabout 40 to about 100 seconds, preferably for about 70 to about 80seconds, a core is lowered at a controlled speed into the gellingreacting mixture.

A ball cup holds the ball core through reduced pressure (or partialvacuum). Upon location of the core in the halves of the mold aftergelling for about 4 to about 12 seconds, the vacuum is released allowingthe core to be released. In one embodiment, the vacuum is releasedallowing the core to be released after about 5 seconds to 10 seconds.The mold halves, with core and solidified cover half thereon, areremoved from the centering fixture unit, inverted and mated with secondmold halves which, at an appropriate time earlier, have had a selectedquantity of reacting prepolymer and curing agent introduced therein tocommence gelling.

Similarly, U.S. Pat. No. 5,006,297 and U.S. Pat. No. 5,334,673 both alsodisclose suitable molding techniques that may be utilized to apply thepolyurea-based and polyurethane-based compositions of the invention.However, the method of the invention is not limited to the use of thesetechniques; other methods known to those skilled in the art may also beemployed. For instance, other methods for holding the ball core may beutilized instead of using a partial vacuum.

Dimples

The use of various dimple patterns and profiles provides a relativelyeffective way to modify the aerodynamic characteristics of a golf ball.As such, the manner in which the dimples are arranged on the surface ofthe ball can be by any available method. For instance, the ball may havean icosahedron-based pattern, such as described in U.S. Pat. No.4,560,168, or an octahedral-based dimple patterns as described in U.S.Pat. No. 4,960,281. Alternatively, the dimple pattern can be arrangedaccording to phyllotactic patterns, such as described in U.S. Pat. No.6,338,684, which is incorporated herein in its entirety.

Dimple patterns may also be based on Archimedean patterns including atruncated octahedron, a great rhombcuboctahedron, a truncateddodecahedron, and a great rhombicosidodecahedron, wherein the patternhas a non-linear parting line, as disclosed in U.S. Patent PublicationNo. 2003/0158001, which is incorporated by reference herein.

The golf balls of the present invention may also be covered withnon-circular shaped dimples, i.e., amorphous shaped dimples, asdisclosed in U.S. Pat. No. 6,409,615, which is incorporated in itsentirety by reference herein.

Dimple patterns that provide a high percentage of surface coverage arepreferred, and are well known in the art. For example, U.S. Pat. Nos.5,562,552, 5,575,477, 5,957,787, 5,249,804, and 4,925,193 disclosegeometric patterns for positioning dimples on a golf ball so as toprovide a high degree of surface coverage. In addition, a tubularlattice pattern, such as the one disclosed in U.S. Pat. No. 6,290,615,which is incorporated by reference in its entirety herein, may also beused with golf balls of the present invention. The golf balls of thepresent invention may also have a plurality of pyramidal projectionsdisposed on the intermediate layer of the ball, as disclosed in U.S.Pat. No. 6,383,092, which is incorporated in its entirety by referenceherein.

Several additional non-limiting examples of dimple patterns with varyingsizes of dimples are also provided in U.S. Pat. Nos. 6,358,161 and6,213,898, the entire disclosures of which are incorporated by referenceherein.

Dimple profiles revolving a catenary curve about its symmetrical axismay increase aerodynamic efficiency, provide a convenient way to alterthe dimples to adjust ball performance without changing the dimplepattern, and result in uniformly increased flight distance for golfersof all swing speeds. Thus, catenary curve dimple profiles, as disclosedin U.S. Patent Publication No. 2003/0114255, which is incorporated inits entirety by reference herein, is contemplated for use with the golfballs of the present invention.

Golf Ball Post-Processing

The golf balls of the present invention may be painted, coated, orsurface treated for further benefits. For example, golf balls coversfrequently contain a fluorescent material and/or a dye or pigment toachieve the desired color characteristics. A golf ball of the inventionmay also be treated with a base resin paint composition. In addition,the golf ball may be coated with a composition including a whiteningagent.

In one embodiment, the golf balls of the invention may be UV cured.Suitable methods for UV curing are disclosed in U.S. Pat. Nos.6,500,495, 6,248,804, and 6,099,415, the entire disclosures of which areincorporated by reference herein. In one embodiment, the top coat is UVcurable. In another embodiment, the ink is UV curable and may be used asa paint layer or as a discrete marking tool for logos and indicias.

In addition, trademarks or other indicia may be stamped, i.e.,pad-printed, on the outer surface of the ball cover, and the stampedouter surface is then treated with at least one clear coat to give theball a glossy finish and protect the indicia stamped on the cover.

The golf balls of the invention may also be subjected to dyesublimation, wherein at least one golf ball component is subjected to atleast one sublimating ink that migrates at a depth into the outersurface and forms an indicia. The at least one sublimating inkpreferably includes at least one of an azo dye, a nitroarylamine dye, oran anthraquinone dye. U.S. Patent Publication No. 2003/0106442, theentire disclosure of which is incorporated by reference herein.

Laser marking of a selected surface portion of a golf ball causing thelaser light-irradiated portion to change color is also contemplated foruse with the present invention. U.S. Pat. Nos. 5,248,878 and 6,075,223generally disclose such methods, the entire disclosures of which areincorporated by reference herein. In addition, the golf balls may besubjected to ablation, i.e., directing a beam of laser radiation onto aportion of the cover, irradiating the cover portion, wherein theirradiated cover portion is ablated to form a detectable mark, whereinno significant discoloration of the cover portion results therefrom.Ablation is discussed in U.S. Pat. No. 6,462,303, which is incorporatedin its entirety by reference herein.

Protective and decorative coating materials, as well as methods ofapplying such materials to the surface of a golf ball cover are wellknown in the golf ball art. Generally, such coating materials compriseurethanes, urethane hybrids, epoxies, polyesters and acrylics. Ifdesired, more than one coating layer can be used. The coating layer(s)may be applied by any suitable method known to those of ordinary skillin the art. In one embodiment, the coating layer(s) is applied to thegolf ball cover by an in-mold coating process, such as described in U.S.Pat. No. 5,849,168, which is incorporated in its entirety by referenceherein.

The use of the polyurea-based and polyurethane-based compositions ingolf equipment may reduce, or completely obviate, the need for typicalpost-processing, e.g., coating a golf ball with a pigmented coatingprior to applying a clear topcoat to the ball. Unlike compositions withno light stable properties, the compositions used in forming the golfequipment of the present invention do not discolor upon exposure tolight (especially in the case of extended exposure). Also, byeliminating at least one coating step, the manufacturer realizeseconomic benefits in terms of reduced process times and consequentimproved labor efficiency. Further, significant reduction in volatileorganic compounds (“VOCs”), typical constituents of paint, may berealized through the use of the present invention, offering significantenvironmental benefits.

Thus, while it may not be necessary to use pigmented coating on the golfballs of the present invention when formed with the compositions of theinvention, the golf balls of the present invention may be painted,coated, or surface treated for further benefits. For example, the valueof golf balls made according to the invention and painted offer enhancedcolor stability as degradation of the surface paint occurs during thenormal course of play. The mainstream technique used nowadays forhighlighting whiteness is to form a cover toned white with titaniumdioxide, subjecting the cover to such surface treatment as coronatreatment, plasma treatment, UV treatment, flame treatment, or electronbeam treatment, and applying one or more layers of clear paint, whichmay contain a fluorescent whitening agent. This technique is productiveand cost effective.

Golf Ball Properties

The properties such as hardness, modulus, core diameter, intermediatelayer thickness and cover layer thickness of the golf balls of thepresent invention have been found to effect play characteristics such asspin, initial velocity and feel of the present golf balls. For example,the flexural and/or tensile modulus of the intermediate layer arebelieved to have an effect on the “feel” of the golf balls of thepresent invention. It should be understood that the ranges herein aremeant to be intermixed with each other, i.e., the low end of one rangemay be combined with a high end of another range.

Component Dimensions

Dimensions of golf ball components, i.e., thickness and diameter, mayvary depending on the desired properties. For the purposes of theinvention, any layer thickness may be employed. Non-limiting examples ofthe various embodiments outlined above are provided here with respect tolayer dimensions.

The present invention relates to golf balls of any size. While USGAspecifications limit the size of a competition golf ball to more than1.68 inches in diameter, golf balls of any size can be used for leisuregolf play. The preferred diameter of the golf balls is from about 1.68inches to about 1.8 inches. The more preferred diameter is from about1.68 inches to about 1.76 inches. A diameter of from about 1.68 inchesto about 1.74 inches is most preferred, however diameters anywhere inthe range of from 1.7 to about 1.95 inches can be used. Preferably, theoverall diameter of the core and all intermediate layers is about 80percent to about 98 percent of the overall diameter of the finishedball.

The core may have a diameter ranging from about 0.09 inches to about1.65 inches. In one embodiment, the diameter of the core of the presentinvention is about 1.2 inches to about 1.630 inches. In anotherembodiment, the diameter of the core is about 1.3 inches to about 1.6inches, preferably from about 1.39 inches to about 1.6 inches, and morepreferably from about 1.5 inches to about 1.6 inches. In yet anotherembodiment, the core has a diameter of about 1.55 inches to about 1.65inches.

The core of the golf ball may also be extremely large in relation to therest of the ball. For example, in one embodiment, the core makes upabout 90 percent to about 98 percent of the ball, preferably about 94percent to about 96 percent of the ball. In this embodiment, thediameter of the core is preferably about 1.54 inches or greater,preferably about 1.55 inches or greater. In one embodiment, the corediameter is about 1.59 inches or greater. In another embodiment, thediameter of the core is about 1.64 inches or less.

When the core includes an inner core layer and an outer core layer, theinner core layer is preferably about 0.9 inches or greater and the outercore layer preferably has a thickness of about 0.1 inches or greater. Inone embodiment, the inner core layer has a diameter from about 0.09inches to about 1.2 inches and the outer core layer has a thickness fromabout 0.1 inches to about 0.8 inches. In yet another embodiment, theinner core layer diameter is from about 0.095 inches to about 1.1 inchesand the outer core layer has a thickness of about 0.20 inches to about0.03 inches.

The cover typically has a thickness to provide sufficient strength, goodperformance characteristics, and durability. In one embodiment, thecover thickness is from about 0.02 inches to about 0.35 inches. Thecover preferably has a thickness of about 0.02 inches to about 0.12inches, preferably about 0.1 inches or less. When the compositions ofthe invention are used to form the outer cover of a golf ball, the covermay have a thickness of about 0.1 inches or less, preferably about 0.07inches or less. In one embodiment, the outer cover has a thickness fromabout 0.02 inches to about 0.07 inches. In another embodiment, the coverthickness is about 0.05 inches or less, preferably from about 0.02inches to about 0.05 inches. In yet another embodiment, the outer coverlayer of such a golf ball is between about 0.02 inches and about 0.045inches. In still another embodiment, the outer cover layer is about0.025 to about 0.04 inches thick. In one embodiment, the outer coverlayer is about 0.03 inches thick.

The range of thicknesses for an intermediate layer of a golf ball islarge because of the vast possibilities when using an intermediatelayer, i.e., as an outer core layer, an inner cover layer, a woundlayer, a moisture/vapor barrier layer. When used in a golf ball of theinvention, the intermediate layer, or inner cover layer, may have athickness about 0.3 inches or less. In one embodiment, the thickness ofthe intermediate layer is from about 0.002 inches to about 0.1 inches,preferably about 0.01 inches or greater. In one embodiment, thethickness of the intermediate layer is about 0.09 inches or less,preferably about 0.06 inches or less. In another embodiment, theintermediate layer thickness is about 0.05 inches or less, morepreferably about 0.01 inches to about 0.045 inches. In one embodiment,the intermediate layer, thickness is about 0.02 inches to about 0.04inches. In another embodiment, the intermediate layer thickness is fromabout 0.025 inches to about 0.035 inches. In yet another embodiment, thethickness of the intermediate layer is about 0.035 inches thick. Instill another embodiment, the inner cover layer is from about 0.03inches to about 0.035 inches thick. Varying combinations of these rangesof thickness for the intermediate and outer cover layers may be used incombination with other embodiments described herein.

The ratio of the thickness of the intermediate layer to the outer coverlayer is preferably about 10 or less, preferably from about 3 or less.In another embodiment, the ratio of the thickness of the intermediatelayer to the outer cover layer is about 1 or less. The core andintermediate layer(s) together form an inner ball preferably having adiameter of about 1.48 inches or greater for a 1.68-inch ball. In oneembodiment, the inner ball of a 1.68-inch ball has a diameter of about1.52 inches or greater. In another embodiment, the inner ball of a1.68-inch ball has a diameter of about 1.66 inches or less. In yetanother embodiment, a 1.72-inch (or more) ball has an inner balldiameter of about 1.50 inches or greater. In still another embodiment,the diameter of the inner ball for a 1.72-inch ball is about 1.70 inchesor less.

Hardness

Most golf balls consist of layers having different hardnesses, e.g.,hardness gradients, to achieve desired performance characteristics. Thepresent invention contemplates golf balls having hardness gradientsbetween layers, as well as those golf balls with layers having the samehardness.

It should be understood, especially to one of ordinary skill in the art,that there is a fundamental difference between “material hardness” and“hardness, as measured directly on a golf ball.” Material hardness isdefined by the procedure set forth in ASTM-D2240 and generally involvesmeasuring the hardness of a flat “slab” or “button” formed of thematerial of which the hardness is to be measured. Hardness, whenmeasured directly on a golf ball (or other spherical surface) is acompletely different measurement and, therefore, results in a differenthardness value. This difference results from a number of factorsincluding, but not limited to, ball construction (i.e., core type,number of core and/or cover layers, etc.), ball (or sphere) diameter,and the material composition of adjacent layers. It should also beunderstood that the two measurement techniques are not linearly relatedand, therefore, one hardness value cannot easily be correlated to theother.

The cores of the present invention may have varying hardnesses dependingon the particular golf ball construction. In one embodiment, the corehardness is at least about 15 Shore A, preferably about 30 Shore A, asmeasured on a formed sphere. In another embodiment, the core has ahardness of about 50 Shore A to about 90 Shore D. In yet anotherembodiment, the hardness of the core is about 80 Shore D or less.Preferably, the core has a hardness about 30 to about 65 Shore D, andmore preferably, the core has a hardness about 35 to about 60 Shore D.

The intermediate layer(s) of the present invention may also vary inhardness depending on the specific construction of the ball. In oneembodiment, the hardness of the intermediate layer is about 30 Shore Dor greater. In another embodiment, the hardness of the intermediatelayer is about 90 Shore D or less, preferably about 80 Shore D or less,and more preferably about 70 Shore D or less. In yet another embodiment,the hardness of the intermediate layer is about 50 Shore D or greater,preferably about 55 Shore D or greater. In one embodiment, theintermediate layer hardness is from about 55 Shore D to about 65 ShoreD. The intermediate layer may also be about 65 Shore D or greater.

When the intermediate layer is intended to be harder than the corelayer, the ratio of the intermediate layer hardness to the core hardnesspreferably about 2 or less. In one embodiment, the ratio is about 1.8 orless. In yet another embodiment, the ratio is about 1.3 or less.

As with the core and intermediate layers, the cover hardness may varydepending on the construction and desired characteristics of the golfball. The ratio of cover hardness to inner ball hardness is a primaryvariable used to control the aerodynamics of a ball and, in particular,the spin of a ball. In general, the harder the inner ball, the greaterthe driver spin and the softer the cover, the greater the driver spin.

For example, when the intermediate layer is intended to be the hardestpoint in the ball, e.g., about 50 Shore D to about 75 Shore D, the covermaterial may have a hardness of about 20 Shore D or greater, preferablyabout 25 Shore D or greater, and more preferably about 30 Shore D orgreater, as measured on the slab. In another embodiment, the coveritself has a hardness of about 30 Shore D or greater. In particular, thecover may be from about 30 Shore D to about 70 Shore D. In oneembodiment, the cover has a hardness of about 40 Shore D to about 65Shore D, and in another embodiment, about 40 Shore to about 55 Shore D.In another aspect of the invention, the cover has a hardness less thanabout 45 Shore D, preferably less than about 40 Shore D, and morepreferably about 25 Shore D to about 40 Shore D. In one embodiment, thecover has a hardness from about 30 Shore D to about 40 Shore D.

In this embodiment when the outer cover layer is softer than theintermediate layer or inner cover layer, the ratio of the Shore Dhardness of the outer cover material to the intermediate layer materialis about 0.8 or less, preferably about 0.75 or less, and more preferablyabout 0.7 or less. In another embodiment, the ratio is about 0.5 orless, preferably about 0.45 or less.

In yet another embodiment, the ratio is about 0.1 or less when the coverand intermediate layer materials have hardnesses that are substantiallythe same. When the hardness differential between the cover layer and theintermediate layer is not intended to be as significant, the cover mayhave a hardness of about 55 Shore D to about 65 Shore D. In thisembodiment, the ratio of the Shore D hardness of the outer cover to theintermediate layer is about 1.0 or less, preferably about 0.9 or less.

The cover hardness may also be defined in terms of Shore C. For example,the cover may have a hardness of about 70 Shore C or greater, preferablyabout 80 Shore C or greater. In another embodiment, the cover has ahardness of about 95 Shore C or less, preferably about 90 Shore C orless.

In another embodiment, the cover layer is harder than the intermediatelayer. In this design, the ratio of Shore D hardness of the cover layerto the intermediate layer is about 1.33 or less, preferably from about1.14 or less.

When a two-piece ball is constructed, the core may be softer than theouter cover. For example, the core hardness may range from about 30Shore D to about 50 Shore D, and the cover hardness may be from about 50Shore D to about 80 Shore D. In this type of construction, the ratiobetween the cover hardness and the core hardness is preferably about1.75 or less. In another embodiment, the ratio is about 1.55 or less.Depending on the materials, for example, if a composition of theinvention is acid-functionalized wherein the acid groups are at leastpartially neutralized, the hardness ratio of the cover to core ispreferably about 1.25 or less.

Compression

Compression values are dependent on the diameter of the component beingmeasured. The Atti compression of the core, or portion of the core, ofgolf balls prepared according to the invention is preferably less thanabout 80, more preferably less than about 75. As used herein, the terms“Atti compression” or “compression” are defined as the deflection of anobject or material relative to the deflection of a calibrated spring, asmeasured with an Atti Compression Gauge, that is commercially availablefrom Atti Engineering Corp. of Union City, N.J. Atti compression istypically used to measure the compression of a golf ball. In anotherembodiment, the core compression is from about 40 to about 80,preferably from about 50 to about 70. In yet another embodiment, thecore compression is preferably below about 50, and more preferably belowabout 25.

In an alternative, low compression embodiment, the core has acompression less than about 20, more preferably less than about 10, andmost preferably, 0. As known to those of ordinary skill in the art,however, the cores generated according to the present invention may bebelow the measurement of the Atti Compression Gauge.

In one embodiment, golf balls of the invention preferably have an Atticompression of about 55 or greater, preferably from about 60 to about120. In another embodiment, the Atti compression of the golf balls ofthe invention is at least about 40, preferably from about 50 to 120, andmore preferably from about 60 to 100. In yet another embodiment, thecompression of the golf balls of the invention is about 75 or greaterand about 95 or less. For example, a preferred golf ball of theinvention may have a compression from about 80 to about 95.

Initial Velocity and COR

There is currently no USGA limit on the COR of a golf ball, but theinitial velocity of the golf ball cannot exceed 250±5 feet/second(ft/s). Thus, in one embodiment, the initial velocity is about 245 ft/sor greater and about 255 ft/s or greater. In another embodiment, theinitial velocity is about 250 ft/s or greater. In one embodiment, theinitial velocity is about 253 ft/s to about 254 ft/s. In yet anotherembodiment, the initial velocity is about 255 ft/s. While the currentrules on initial velocity require that golf ball manufacturers staywithin the limit, one of ordinary skill in the art would appreciate thatthe golf ball of the invention would readily convert into a golf ballwith initial velocity outside of this range.

As a result, of the initial velocity limitation set forth by the USGA,the goal is to maximize COR without violating the 255 ft/s limit. TheCOR of a ball is measured by taking the ratio of the outbound or reboundvelocity to the incoming or inbound velocity. In a one-piece solid golfball, the COR will depend on a variety of characteristics of the ball,including its composition and hardness. For a given composition, CORwill generally increase as hardness is increased. In a two-piece solidgolf ball, e.g., a core and a cover, one of the purposes of the cover isto produce a gain in COR over that of the core. When the contribution ofthe core to high COR is substantial, a lesser contribution is requiredfrom the cover. Similarly, when the cover contributes substantially tohigh COR of the ball, a lesser contribution is needed from the core.

The present invention contemplates golf balls having CORs from about0.700 to about 0.850 at an inbound velocity of about 125 ft/sec. In oneembodiment, the COR is about 0.750 or greater, preferably about 0.780 orgreater. In another embodiment, the ball has a COR of about 0.800 orgreater. In yet another embodiment, the COR of the balls of theinvention is about 0.800 to about 0.815.

In addition, the inner ball preferably has a COR of about 0.780 or more.In one embodiment, the COR is about 0.790 or greater.

Spin Rate

As known to those of ordinary skill in the art, the spin rate of a golfball will vary depending on the golf ball construction. In a multilayerball, e.g., a core, an intermediate layer, and a cover, wherein thecover is formed from the polyurea or polyurethane compositions of theinvention, the spin rate of the ball off a driver (“driver spin rate”)is preferably about 2700 rpm or greater. In one embodiment, the driverspin rate is about 2800 rpm to about 3500 rpm. In another embodiment,the driver spin rate is about 2900 rpm to about 3400 rpm. In stillanother embodiment, the driver spin rate may be less than about 2700rpm.

Two-piece balls made according to the invention may also have driverspin rates of 2700 rpm and greater. In one embodiment, the driver spinrate is about 2700 rpm to about 3300 rpm. Wound balls made according tothe invention may have similar spin rates.

Methods of determining the spin rate should be well understood by thoseof ordinary skill in the art. Examples of methods for determining thespin rate are disclosed in U.S. Pat. Nos. 6,500,073, 6,488,591,6,286,364, and 6,241,622, which are incorporated by reference herein intheir entirety.

Flexural Modulus

Accordingly, it is preferable that the golf balls of the presentinvention have an intermediate layer with a flexural modulus of about500 psi to about 500,000 psi. More preferably, the flexural modulus ofthe intermediate layer is about 1,000 psi to about 250,000 psi. Mostpreferably, the flexural modulus of the intermediate layer is about2,000 psi to about 200,000 psi.

The flexural modulus of the cover layer is preferably about 2,000 psi orgreater, and more preferably about 5,000 psi or greater. In oneembodiment, the flexural modulus of the cover is from about 10,000 psito about 150,000 psi. More preferably, the flexural modulus of the coverlayer is about 15,000 psi to about 120,000 psi. Most preferably, theflexural modulus of the cover layer is about 18,000 psi to about 110,000psi. In another embodiment, the flexural modulus of the cover layer isabout 100,000 psi or less, preferably about 80,000 or less, and morepreferably about 70,000 psi or less. For example, the flexural modulusof the cover layer may be from about 10,000 psi to about 70,000 psi,from about 12,000 psi to about 60,000 psi, or from about 14,000 psi toabout 50,000 psi.

In one embodiment, when the cover layer has a hardness of about 50 ShoreD to about 60 Shore D, the cover layer preferably has a flexural modulusof about 55,000 psi to about 65,000 psi.

In one embodiment, the ratio of the flexural modulus of the intermediatelayer to the cover layer is about 0.003 to about 50. In anotherembodiment, the ratio of the flexural modulus of the intermediate layerto the cover layer is about 0.006 to about 4.5. In yet anotherembodiment, the ratio of the flexural modulus of the intermediate layerto the cover layer is about 0.11 to about 4.5.

In one embodiment, the compositions of the invention are used in a golfball with multiple cover layers having essentially the same hardness,but differences in flexural moduli. In this aspect of the invention, thedifference between the flexural moduli of the two cover layers ispreferably about 5,000 psi or less. In another embodiment, thedifference in flexural moduli is about 500 psi or greater. In yetanother embodiment, the difference in the flexural moduli between thetwo cover layers, wherein at least one is reinforced is about 500 psi toabout 10,000 psi, preferably from about 500 psi to about 5,000 psi. Inone embodiment, the difference in flexural moduli between the two coverlayers formed of unreinforced or unmodified materials is about 1,000 psito about 2,500 psi.

Specific Gravity

The specific gravity of a cover or intermediate layer is preferably atleast about 0.7. In one embodiment, the specific gravity of theintermediate layer or cover is about 0.8 or greater, preferably about0.9 or greater. For example, in one embodiment, the golf ball has anintermediate layer with a specific gravity of about 0.9 or greater and acover having a specific gravity of about 0.95 or greater. In anotherembodiment, the intermediate layer or cover has a specific gravity ofabout 1.00 or greater. In yet another embodiment, the specific gravityof the intermediate layer or cover is about 1.05 or greater, preferablyabout 1.10 or greater.

The core may have a specific gravity of about 1.00 or greater,preferably 1.05 or greater. For example, a golf ball of the inventionmay have a core with a specific gravity of about 1.10 or greater and acover with a specific gravity of about 0.95 or greater.

Adhesion Strength

The adhesion, or peel, strength of the compositions of the invention ispreferably about 5 lb_(f)/in or greater. In one embodiment, the adhesionstrength is about 25 lb_(f)/in or less. For example, the adhesionstrength is preferably about 10 lb_(f)/in or more and about 20 lb_(f)/inor less. In another embodiment, the adhesion strength is about 20lb_(f)/in or greater, preferably about 24 lb_(f)/in or greater. In yetanother embodiment, the adhesion strength is about 26 lb_(f)/in orgreater. In still another embodiment, the adhesion strength is about 20lb_(f)/in to about 30 lb_(f)/in.

Skilled artisans are aware of methods to determine adhesion strength.For example, cross-hatch tests and repeated ball impact tests are usefulto determine the adhesion strength of a particular layer of a golf ball.The cross-hatch test consists of cutting the material into small piecesin mutually perpendicular directions, applying a piece of adhesivecellophane tape over the material, rapidly pulling off the tape, andcounting the number of pieces removed. The repeated impact test consistsof subjecting the finished golf ball to impact repeatedly and visuallyexamining the coating film for peeling from the golf ball. Examples ofthese methods are provided in U.S. Pat. No. 5,316,730, which isincorporated by reference herein.

Moisture Vapor Transmission

The moisture vapor transmission of a golf ball portion formed from thecompositions of the invention may be expressed in terms of absorption,e.g., weight gain or size gain over a period of time at a specificconditions, and transmission, e.g., moisture vapor transmission rate(MVTR) according to ASTM E96-00. MVTR refers to the mass of water vaporthat diffused into a material of a given thickness per unit area perunit time at a specific temperature and humidity differential. Forexample, weight changes of a golf ball portion monitored over a periodof seven weeks in 100 percent relative humidity and 72° F. help todemonstrate which balls have better water resistance. In one embodiment,the golf ball portions of the invention have a weight gain of about 0.15grams or less after seven weeks. In another embodiment, the golf ballsof the invention have a weight gain of about 0.13 grams or less after aseven-week storage period. In still another embodiment, the weight gainof the golf balls of the invention is about 0.09 grams or less afterseven weeks. In yet another embodiment, the weight gain is about 0.06grams or less after a seven-week period. The golf balls of the inventionpreferably have a weight gain of about 0.03 grams or less over aseven-week storage period.

Size gain may also be used as an indicator of water resistance. That is,the more water a golf ball takes on, the larger a golf ball becomes dueto the water enclosed beneath the outermost layer of the golf ballportion. Thus, the golf balls of the invention preferably have noappreciable size gain. In one embodiment, the size gain of the golfballs of the invention after a seven-week period is about 0.001 inchesor less.

MVTR of a golf ball, or portion thereof, may be about 2 g/(m²×day) orless, such as about 0.45 to about 0.95 g/(m²×day), about 0.01 to about0.9 g/(m²×day) or less, at 38° C. and 90 percent relative humidity.

Shear/Cut Resistance

The cut resistance of a golf ball cover may be determined using a sheartest having a scale from 1 to 9 assessing damage and appearance. In oneembodiment, the damage rank is preferably about 3 or less, morepreferably about 2 or less. In another embodiment, the damage rank isabout 1 or less. The appearance rank of a golf ball of the invention ispreferably about 3 or less. In one embodiment, the appearance rank isabout 2 or less, preferably about 1 or less.

Light Stability

The light stability of the cover may be quantified by the difference inyellowness index (ΔYI), i.e., yellowness measured after a predeterminedexposure time—yellowness before exposure. In one embodiment, the ΔYI isabout 10 or less after 5 days (120 hours) of exposure, preferably about6 or less after 5 days of exposure, and more preferably about 4 or lessafter 5 days of exposure. In one embodiment, the ΔYI is about 2 or lessafter 5 days of exposure, and more preferably about 1 or less after 5days of exposure. The difference in the b chroma dimension (Δb*, yellowto blue) is also a way to quantify the light stability of the cover. Inone embodiment, the Δb* is about 4 or less after 5 days (120 hours) ofexposure, preferably about 3 or less after 5 days of exposure, and morepreferably about 2 or less after 5 days of exposure. In one embodiment,the Δb* is about 1 or less after 5 days of exposure.

EXAMPLES

The following non-limiting examples are merely illustrative of thepreferred embodiments of the present invention, and are not to beconstrued as limiting the invention, the scope of which is defined bythe appended claims. Parts are by weight unless otherwise indicated.

Example 1 Saturated Polyurethane Golf Ball Cover

Table 3 illustrates the components used to make a saturated polyurethanegolf ball cover composition. TABLE 3 COMPOSITION Chemicals Weight (g)H₁₂MDI Prepolymer* 458.73 1,4-Butanediol 42.75 HCC-19584 ColorDispersion** 17.55*Prepolymer is the reaction product of 4,4′-dicyclohexylmethanediisocyanate and polytetramethylene ether glycol.**HCC-19584 is a white-blue color dispersion manufactured by the PolyOneCorporation (formerly the Harwick Chemical Corporation)

A golf ball was made having the cover formulated from the compositionabove following the teachings of U.S. Pat. No. 5,733,428. The physicalproperties and the ball performance results are listed in Table 4. TABLE4 PHYSICAL PROPERTIES Physical Properties Present Invention CoverHardness 54 Weight (g) 45.58 Compression 89 Shear Resistance Good ColorStability Comparable to SURLYN ®The molded balls from the above composition listed in Table 4 werefurther subject to a QUV test as described below:Method:

ASTM G 53-88 “Standard Practice for Operating Light and Water-ExposureApparatus (Fluorescent UV-Condensation Type) for Exposure of NonmetallicMaterials” was followed with certain modifications as described below:

Six balls of each variety under evaluation were placed in custom madegolf ball holders and inserted into the sample rack of a Q-PANEL modelOUV/SER Accelerated Weathering Tester manufactured by Q-Panel LabProducts of Cleveland, Ohio. The sample holders were constructed suchthat each ball was approximately 1.75 inches from an UVA-340 bulb, atits closest point. The weathering tester was then cycled every fourhours between the following two sets of conditions (for the specifiedtotal length of time 24, 48, and 120 hours):

-   -   Condition #1: water bath temperature of about 50° C. with the UV        lamps on, set and controlled at an irradiance power of 1.00        W/m²/nm.    -   Condition #2: water bath temperature of about 40° C. with the UV        lamps turned off.        Color was measured before weathering and after each time cycle        using a BYK-Gardner Model TCS II sphere type Spectrophotometer        equipped with a 25-mm port. A D65/10° illumination was used in        the specular reflectance included mode.

The test results for the molded balls after 24 hours of UV exposure aretabulated in Table 5, wherein ΔL* equals the difference in L dimension(light to dark), Δa* equals the difference in the a chroma dimension(red to green), Δb* equals the difference in the b chroma dimension(yellow to blue), ΔC* equals the combined chroma difference (a* and b*scales), hue and saturation, ΔH* equals the total hue difference,excluding effects of saturation and luminescence, ΔE* equals the totalcolor difference, ΔWI equals the difference in the whiteness index, andΔYI and the difference in the yellowness index. TABLE 5 UV STABILITYDATA ΔWI ΔYI Sample ΔL* Δa* Δb* ΔC* ΔH* ΔE* (E313) (D1925) MoldedAliphatic −0.21 −0.30 1.54 −1.26 −0.94 1.58 −9.07 2.99 PolyurethaneMolded Aromatic −17.27 11.36 46.14 47.31 4.36 50.56 −142.35 93.80Polyurethane Molded −0.39 −0.25 0.91 −0.76 −0.55 1.02 −6.19 1.69SURLYN ®

The test results for the molded balls after 48 hours of UV exposure areillustrated in Table 6. TABLE 6 UV STABILITY DATA ΔWI ΔYI Sample ΔL* Δa*Δb* ΔC* HΔ* ΔE* (E313) (D1925) Molded Aliphatic −0.48 −0.37 2.54 −2.02−1.59 2.61 −15.16 4.98 Polyurethane Molded Aromatic −23.46 15.01 42.7545.18 3.44 51.02 −127.75 98.96 Polyurethane Molded −0.54 −0.39 1.43−1.18 −0.91 1.58 −9.50 2.66 SURLYN ®

The test results for the molded balls after 120 hours of UV exposure areillustrated in Table 7. TABLE 7 UV STABILITY DATA ΔWI ΔYI Sample ΔL* Δa*Δb* ΔC* ΔH* ΔE* (E313) (D1925) Molded Aliphatic −0.92 −0.46 5.87 −3.01−5.06 5.96 −33.72 11.68 Polyurethane Molded Aromatic −30.06 16.80 33.3737.29 2.11 47.95 −107.12 94.42 Polyurethane Molded −0.99 −0.85 4.06−2.91 −2.96 4.26 −24.88 7.73 SURLYN ®

Example 2 H₁₂MDI Polyether Urea Cured with Diol

A golf ball was made having the cover formulated from a compositionincluding a prepolymer formed of H₁₂MDI and polyoxyalkylene, having amolecular weight of about 2000, cured with 1,4-butanediol. The physicalproperties and the ball performance results are listed in Table 8. Agolf ball similar to Example 1, a light stable, aliphatic polyurethane,was used for comparison purposes. TABLE 8 PHYSICAL PROPERTIES AliphaticPolyurethane Ball Properties/Ball Types Control Invention NameplateAverage 1.686 1.684 Equator Average 1.684 1.683 Weight Average, oz 1.5991.595 Compression Average 86 86 COR @ 125 ft/sec 0.807 0.805 Cold CrackTest, 5° F. no failure no failure Light Stability (5 Days QUV Test) ΔYI3.2 0.8 Δb* 1.7 0.4 Live Golfer Shear Test* Damage Rank 3 2 AppearanceRank 3 2*Rating of Shear Test: Based on a scale of 1-9, 1 is the best, 9 is theworst.

Example 3 H₁₂MDI Polyether Urea Cured with a Diamine

A golf ball was made having the cover formulated from a compositionincluding a prepolymer formed of H₁₂MDI and polyoxyalkylene, having amolecular weight of about 2000, cured with4,4′-bis-(sec-butylamino)-dicyclohexylmethane (Clearlink 1000). Thephysical properties and the ball performance results are listed in Table9. A golf ball similar to Example 1, a light stable, aliphaticpolyurethane, was used for comparison purposes. TABLE 9 PHYSICALPROPERTIES Light Stable Ball Properties/Ball Types Polyurethane ControlInvention Nameplate Average 1.683 1.686 Equator Average 1.681 1.684Weight Average, oz 1.597 1.600 Compression Average 89 92 COR @ 125ft/sec 0.807 0.815 Cold Crack Test, 5° F. no failure no failure LightStability (5 Days QUV Test) ΔYI 4.3 0.6 Δb* 2.4 0.3 Live Golfer ShearTest* Damage Rank 3 1 Appearance Rank 3 1*Rating of Shear Test: Based on a scale of 1-9, 1 is the best, 9 is theworst.

Example 4 H₁₂MDI Amine-Terminated Compound Urea Cured with a Diamine

A golf ball according to the invention may be made having a cover formedfrom a composition including a prepolymer formed of H₁₂MDI and anamine-terminated compound, such as amine-terminated polybutadiene, curedwith N,N′-diisopropyl-isophorone diamine (JEFFLINK® 754, available fromHuntsman Corporation). The physical properties and the ball performanceresults are listed in Table 9. A control golf ball similar to Example 1,a light stable, aliphatic polyurethane, may be used for comparisonpurposes. The golf ball of the invention, when compared to the controlball, preferably has a better damage rank and appearance rank, as wellas improved light stability after a 5-day QUV test, while stillmaintaining a higher COR.

Example 5 Moisture Resistance of Invention Golf Balls

The moisture resistance of a golf ball of the invention was measured ascompared to a control golf ball. The cover for the invention golf ballwas formed from a composition including a prepolymer of MDI and hydroxyterminated polybutadiene prepolymer cured with4,4-bis-(secbutylamino)diphenylmethane (UNILINK® 4200, available as fromHuntsman Corporation).

The covers were molded on 1.580 inches wound balls, and were finishedwith a conventional coating. The golf balls were incubated in a 50percent relative humidity and 72° F. environmental chamber for one week,and then weighed and measured. These conditioned balls of the inventionwere then subjected to a 100 percent relative humidity and 72° F.environmental chamber. Weight and size changes were monitored over aperiod of 7 weeks. The results of the tests are tabulated below (Tables10 and 11) and illustrated graphically in FIGS. 9 and 10. TABLE 10WEIGHT GAIN (G) OF URETHANE COVERED BALLS OVER TIME Ball 1 week + 2weeks + Type 4 days 1 week 5 days 4 days 3 weeks 4 weeks 5 weeks 7 weeksControl +0.06 g +0.08 g +0.09 g +0.13 g +0.13 g +0.13 g +0.15 g +0.18 gInvention +0.01 g +0.01 g +0.01 g +0.02 g +0.02 g +0.02 g +0.02 g +0.03g

TABLE 11 SIZE GAIN (INCHES) OF URETHANE COVERED BALLS OVER TIME Ball 1week + 2 weeks + Type 4 days 1 week 5 days 4 days 3 weeks 4 weeks 5weeks 7 weeks Control 0 +0.001 in. +0.001 in. +0.001 in. +0.001 in.+0.001 in. +0.001 in. +0.001 in. Invention 0 0 0 0 0 0 0 0

Example 6 Water Resistant Polyurea-Covered Golf Balls

Golf balls may be made according to the invention using a solid core, anintermediate layer, and a cover formed of a water resistant polyureacomposition. In particular, the covers may be formed from the reactionproduct of a polyurea prepolymer and a curing agent.

The polyurea prepolymer may be formed from an isocyanate, e.g., H₁₂MDI,and an amine-terminated compound having a hydrophobic backbone, e.g., anamine-terminated polybutadiene. The curing agent may be a secondarydiamine, such as 4,4′-bis-(sec-butylamino)-dicyclohexylmethane (UNILINK®4200, available as from Huntsman Corporation),N,N′-diisopropyl-isophorone diamine (JEFFLINK® 754, available fromHuntsman Corporation), or mixtures thereof.

Control balls are preferably formed using the same core and intermediatelayer materials, but using a polyurethane composition that includes apolyol without a hydrophobic backbone. Both the invention golf balls andthe control golf balls may be incubated in a 50 percent relativehumidity and 72° F. environmental chamber for one week, and then weighedand measured. These balls may then be subjected to a 100 percentrelative humidity and 72° F. environmental chamber. Weight and sizechanges may then be monitored over a period of 7 weeks.

The water-resistant polyurea-covered golf balls, when compared to thecontrol balls, will have better water resistance. For example, the golfballs of the invention may have a weight gain of about 75 percent lessthan the control golf balls after seven weeks, preferably about 80percent less weight gain than the control balls. Likewise, the golfballs of the invention preferably have no size gain after seven weeks,whereas the control golf balls, as shown above in Example 5, Table 11,have a size gain of 0.001 inches.

Example 6 Golf Balls Formed from Polyurethane-Based CompositionsIncorporating Block Copolymers

Golf balls may be made according to the invention using a solid core, anintermediate layer, and a cover formed of a polyurethane-basedcomposition of the invention incorporating a block copolymer. Inparticular, the covers may be formed from the reaction product of apolyurethane prepolymer, a block copolymer, a coupling agent, and acuring agent.

The polyurethane prepolymer may be formed from an isocyanate, e.g.,H₁₂MDI, and a hydroxy-terminated compound. The polyurethane prepolymermay be incorporated at the terminal end of a block copolymer, such asSBS block copolymer, using a coupling agent. After the prepolymer iscoupled with the SBS block copolymer, the compound may be cured using ahydroxy-terminated curing agent or an amine-terminated curing agent.

Example 7 Golf Balls Formed from Polyurea-Based CompositionsIncorporating Block Copolymer

Golf balls may be made according to the invention using a solid core, anintermediate layer, and a cover formed of a polyurea-based compositionof the invention incorporating a block copolymer. In particular, thecovers may be formed from the reaction product of a polyurea prepolymer,a block copolymer, a coupling agent, and a curing agent.

The polyurea prepolymer may be formed from an isocyanate, e.g., H₁₂MDI,and an amine-terminated compound. The polyurea prepolymer may beincorporated at the terminal end of a block copolymer, such as SBS blockcopolymer, using a coupling agent. After the prepolymer is coupled withthe SBS block copolymer, the compound may be cured using anamine-terminated curing agent, e.g., a secondary diamine, such as4,4′-bis-(sec-butylamino)-dicyclohexylmethane (UNILINK® 4200, availableas from Huntsman Corporation), N,N′-diisopropyl-isophorone diamine(JEFFLINK® 754, available from Huntsman Corporation), or mixturesthereof.

The invention described and claimed herein is not to be limited in scopeby the specific embodiments herein disclosed, since these embodimentsare intended as illustrations of several aspects of the invention. Anyequivalent embodiments are intended to be within the scope of thisinvention. For example, the compositions of the invention may also beused in golf equipment such as putter inserts, golf club heads andportions thereof, golf shoe portions, and golf bag portions. Indeed,various modifications of the invention in addition to those shown anddescribed herein will become apparent to those skilled in the art fromthe foregoing description. Such modifications are also intended to fallwithin the scope of the appended claims. All patents and patentapplications cited in the foregoing text are expressly incorporateherein by reference in their entirety.

1. A golf ball comprising a core and a cover, wherein at least a portionof the golf ball is cast from a composition comprising the reactionproduct of: a prepolymer comprising the reaction product of: a firstprepolymer and a functionalized block copolymer, wherein the prepolymeris capped by isocyanate end groups, and wherein the functionalized blockcopolymer comprises a hydrophobic A_(x)-B_(y) block or A_(x)-B_(y)-A_(z)block, wherein A comprises an olefin or an acrylate, B comprises adiene, and x, y, and z are independently 1 or greater; and a curingagent, wherein the composition consists essentially of the followinglinkages:

wherein x is about 1 or greater, and R and R₁ comprise a straight chainor branched hydrocarbon chain having about 1 to about 20 carbons.
 2. Thegolf ball of claim 1, wherein the functionalized block copolymercomprises at least one functional group selected from the groupconsisting of hydroxy groups, amino groups, thiol groups, andcombinations thereof.
 3. The golf ball of claim 1, wherein the firstprepolymer comprises an isocyanate and a polyamine.
 4. The golf ball ofclaim 1, wherein the A_(x)-B_(y)-A_(z) block comprisesolefin-diene-olefin.
 5. The golf ball of claim 4, wherein theolefin-diene-olefin is styrene-butadiene-styrene.
 6. The golf ball ofclaim 1, wherein the portion has a moisture vapor transmission rate ofabout 0.01 to about 0.09 g/(m²×day) at 38° C. and 90 percent relativehumidity.
 7. The golf ball of claim 1, wherein the portion of the golfball is a cover layer.
 8. A golf ball comprising a core and a cover,wherein at least a portion of the golf ball is cast from a compositioncomprising the reaction product of: an isocyanate-containing compound;and a functionalized block copolymer comprising the reaction product of:a hydrophobic A_(x)-B_(y) block or A_(x)-B_(y)-A_(z) block, wherein Acomprises an olefin or an acrylate, B comprises a diene, and x, y, and zare independently 1 or greater; and a coupling agent, wherein thecomposition comprises following linkages:

wherein x is about 1 or greater, and R and R₁ comprise a straight chainor branched hydrocarbon chain having about 1 to about 20 carbons.
 9. Thegolf ball of claim 8, wherein the composition consists essentially ofthe following linkages:

wherein x is about 1 or greater, and R and R₁ comprise a straight chainor branched hydrocarbon chain having about 1 to about 20 carbons. 10.The golf ball of claim 8, wherein the A_(x)-B_(y) block comprises anolefin-diene block.
 11. The golf ball of claim 10, wherein theA_(x)-B_(y) block comprises a styrene-butadiene block.
 12. The golf ballof claim 8, wherein the A_(x)-B_(y)-A_(z) block comprisesolefin-diene-olefin.
 13. The golf ball of claim 12, wherein theolefin-diene-olefin is styrene-butadiene-styrene.
 14. The golf ball ofclaim 8, wherein the portion the golf ball comprises a cover layer. 15.The golf ball of claim 8, wherein the cover comprises an inner coverlayer and an outer cover layer disposed about the inner cover layer, andwherein the outer cover layer comprises the composition.
 16. The golfball of claim 15, wherein the inner cover layer comprises athermoplastic material.
 17. A golf ball comprising a core, anintermediate layer, and a cover, wherein the cover is cast from acomposition comprising: a prepolymer comprising: a first prepolymerformed from the reaction product of an isocyanate and anamine-terminated compound; and a block copolymer comprising functionalgroups at each terminal end and a hydrophobic A_(x)-B_(y) block orA_(x)-B_(y)-A_(z) block, wherein A comprises an olefin or an acrylate, Bcomprises a diene, and x, y, and z are independently 1 or greater; andan amine-terminated curing agent.
 18. The golf ball of claim 17, whereinthe curing agent is selected from the group consisting of ethylenediamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyl diamine; 2,2,4-and 2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; 4,4′-dicyclohexylmethane diamine;1,4-cyclohexane-bis-(methylamine); 1,3-cyclohexane-bis-(methylamine);diethylene glycol bis-(aminopropyl)ether;2-methylpentamethylene-diamine; diaminocyclohexane; diethylene triamine;triethylene tetramine; tetraethylene pentamine; propylene diamine;1,3-diaminopropane; dimethylamino propylamine; diethylamino propylamine;imido-bis-propylamine; monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; 4,4′-methylenebis-(2-chloroaniline);3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine;3,5-diethylthio-2,6-toluenediamine;4,4′-bis-(sec-butylamino)-diphenylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-benzene; 1,2-bis-(sec-butylamino)-benzene;N,N′-dialkylamino-diphenylmethane;trimethyleneglycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate;4,4′-methylenebis-(3-chloro-2,6-diethyleneaniline);4,4′-methylenebis-(2,6-diethylaniline); meta-phenylenediamine;paraphenylenediamine; N,N′-diisopropyl-isophoronediamine;polyoxypropylene diamine; propylene oxide-based triamine;3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof. 19.The golf ball of claim 17, wherein the A_(x)-B_(y) block comprises anolefin-diene block.
 20. The golf ball of claim 17, wherein theA_(x)-B_(y)-A_(z) block comprises olefin-diene-olefin.